Nutrient Cycling in Agroecosystems Volume 30 Issue 1 1991 (Doi 10.1007/bf01048832) D. W. Rutland - Fertilizer Caking - Mechanisms, Influential Factors, and Methods of Prevention
Most fertilizers have some tendency to form lumps or agglomerates (caking) during storage. Caking mechanisms, factors that influence caking, and met hods of prevention are discussed. A quality fertilizer should be as free flowing, dust free, and nonhygroscopic as possible.
Original Description:
Original Title
Nutrient Cycling in Agroecosystems Volume 30 Issue 1 1991 [Doi 10.1007%2Fbf01048832] D. W. Rutland -- Fertilizer Caking- Mechanisms, Influential Factors, And Methods of Prevention
Most fertilizers have some tendency to form lumps or agglomerates (caking) during storage. Caking mechanisms, factors that influence caking, and met hods of prevention are discussed. A quality fertilizer should be as free flowing, dust free, and nonhygroscopic as possible.
Nutrient Cycling in Agroecosystems Volume 30 Issue 1 1991 (Doi 10.1007/bf01048832) D. W. Rutland - Fertilizer Caking - Mechanisms, Influential Factors, and Methods of Prevention
Most fertilizers have some tendency to form lumps or agglomerates (caking) during storage. Caking mechanisms, factors that influence caking, and met hods of prevention are discussed. A quality fertilizer should be as free flowing, dust free, and nonhygroscopic as possible.
1991 Kluwer Academic Publishers. Printed in the Netherlands. 99
Fertilizer caking: mechani sms, influential factors, and met hods of preventi on D.W. Rut l and International Fertilizer Development Center (IFDC), P.O. Box 2040, Muscle Shoals, AL 35662, USA Key words: Anticaking agents, caking, coating, conditioners Abstract Most fertilizers have some tendency to form lumps or agglomerates (caking) during storage. The mechani sm of caking in fertilizers is most often attributed to the formation of salt bridges and/ or capillary adhesion. The severity of caking can be influenced by a number of factors, such as chemical composi t i on, moisture content, particle structure, mechanical strength, hygroscopic properties, product t emperat ure, ambi ent conditions, storage time, and storage pressure. The various met hods of reducing or eliminating caking in fertilizers basically involve process control, st orage/ packagi ng conditions, and/ or addition of anticaking agents. Caking mechanisms, factors that influence caking, and met hods of prevention are discussed in this paper. Particular attention is given to the various types of anticaking agents and their modes of action. The paper also provides a fairly comprehensive list of commercially available anticaking agents and their producers. Introduction It is the responsibility of the manufact urer to see that the consumer receives a quality fertilizer. A quality fertilizer should meet not only the specified nutrient requi rement s but also certain ' expect ed' standards of physical quality. There- fore, a fertilizer should be as free flowing, dust free, and nonhygroscopic as possible. Fertilizers, bet ween the time of production and final application to the soil, must be stored, either in bul k or in bags, for periods that can vary from less than a mont h to a year or more. Duri ng this time it is essential that the materials remain free flowing (noncaked). Unfort unat el y, many fertilizers, under certain conditions, t end to cake into hard lumps [1]. Causes of caking Caking of fertilizer is caused by the formation of contact points bet ween the particles (granules, prills, tablets, briquettes, powder, crystals, etc.). These contact points differ in nature and can be divided into t hree types, namely, phase contacts, adhesive contacts, and liquid contacts [2]. Phase contacts (salt bridges) are crystal bridges formed at the contact points bet ween the fertil- izer particles. The most t roubl esome caking of fertilizers is believed to be caused by crystal bridging. Crystal bridges develop during storage as a result of continuing internal chemical re- actions, dissolution/recrystallization processes, and/ or thermal effects. Adhesi ve contacts (capillary adhesion) are formed as a result of molecular attraction be- t ween the surfaces in contact. These forces of attraction, known as Van der Waals forces, are considered to be relatively weak. This type of contact is influenced mostly by the plasticity of the particles and the pressure exert ed on the fertilizer material when it is stacked in bags or piled in bulk. The condition is usually referred to as bag or pile set, and the material normally 100 reverts to a free-flowing form rat her easily with a minimal amount of handling. Liquid contacts are due to considerable wet- ting of the product , which causes films of a sat urat ed solution to form bet ween particles. Format i on of t hese types of contact points is defined as ' sticking' . Al t hough such 'sticking' has little strength, it is obviously undesirable. Fact ors i nf l uenci ng caki ng Caking in fertilizers can be influenced by a num- ber of factors. These factors can be divided into internal factors, related to the physical-chemical constitution of the fertilizer, and external fac- tors, rel at ed to the environmental conditions to which the fertilizer is exposed during handling and storage. Many of these factors are interre- lated [1, 3, 4, 5, 6]. Internal factors The moisture cont ent of the product is usually consi dered to be the most important factor in promot i ng caking. For most caking mechanisms, t he presence of moisture, in the form of solution phases, is essential. Generally, the higher the degree of drying at the time of manufacture, the less active the caking mechanisms will be. The ext ent of drying requi red to effectively inactivate caking mechanisms varies rather widely with the composi t i on and physical makeup of the fertilizer. The chemical composition has an effect on the caking t endency of a fertilizer. For example, it has been shown that the caking t endency of ammoni um ni t rat e-based and urea-based NPK fertilizers is significantly great er than that of ammoni um sulfate-based and ammoni um phos- phat e-based NPK fertilizers. Even impurities may affect caking. The Tennessee Valley Au- thority (TVA) has demonst rat ed that iron and aluminum impurities present in di ammoni um phosphat e are effective in decreasing caking. The size and shape of the particles are also important. If the particles are relatively large, well formed, and uniform in size and shape with very little fine material, the specific surface area is reduced. Consequent l y, forces of attraction and points of contact bet ween adj acent particles are reduced, lowering the tendency to cake. The mechanical strength or hardness of the particles has an effect on the caking tendency. Weak granules may break down under stack or pile pressure (crushing strength) or during handl- ing (abrasion and impact strength). As a result, a substantial quantity of fines can be created, t her eby increasing the number of contact points bet ween particles. The hygroscopic properties of the product can have an effect on the degree of caking. All fertilizers have a maximum relative humidity (re- ferred to as the critical relative humidity [CRH]) above which t hey will absorb moisture. The CRH, a uni que material propert y, is generally l owered when the material contains impurities or is mixed with ot her fertilizer salts. Caking as a result of moisture absorption usually occurs along the pile surface; with prol onged exposure of the material to el evat ed humidities, caking can become quite deep. The hygroscopic nat ure of a fertilizer product , along with product tem- perat ure, ambient t emperat ure, and atmospheric relative humidity, also influences the mass trans- fer of moisture through a bulk pile of fertilizer. Transfer of moisture through a pile of fertilizer can cause severe caking problems. The t emperat ure of the product when placed in storage influences caking tendency. Hi gher t emperat ures increase the chemical reactivity, such as the re-evaporat i on of wat er, which re- sults in recrystallization and formation of solid crystalline bridges. Additionally, a high product t emper at ur e can pr omot e particle plasticity caus- ing the particles to deform under pressure. This deformat i on promot es bot h crystal bridging and capillary adhesion. For example, a report by Nederl andse Stikstof Maatschappij (NSM), a company that has done extensive research on the caking t endency of urea, states, ' Ur ea being fed to the stockpile at 50C to 70C will definitely form strong cakes. The lower the feed tempera- ture, the lower the t endency to cake. ' The con- clusion of the study was that if the prills are cool ed bel ow 30C before entering storage, t here is less agglomeration and, mainly, the agglomer- ates are softer [7].' 101 External factors The warehouse or storage t emperat ure can have an effect on caking t endency in fertilizer. Hi gher ambi ent t emperat ures lower the CRH of a fertil- izer material and t hereby increase its hygros- copicity. For example, the CRH of a 15-15-15 ni t rophosphat e is approximately 55% at 30C, whereas it is approximately 45% at 40C. Con- versely, raising the t emperat ure of existing warehouse air will reduce the relative humidity ( RH) . This met hod is empl oyed to lower the warehouse RH bel ow the CRH of the fertilizer. The humidity of the surrounding at mosphere affects caking. As ment i oned previously, when a fertilizer is exposed to a RH above its CRH, absorpt i on of moisture will t ake place. Saturated solutions will t hen be formed at the granule surface, promot i ng capillary adhesion and crys- tallization processes due to changes in tempera- t ure or subsequent evaporation. Her e the severi- ty of caking depends mainly on the rate of absorpt i on. The rate of absorption is dependent on factors such as: 1. The difference bet ween the RH of the air and t he CRH of the fertilizer; 2. The movement of air with a constant RH over t he fertilizer; 3. The moisture-holding capacity of the fertilizer as influenced by the granulometry and porosi- ty and 4. The rate of penet rat i on into the bulk of fertil- izer [3]. The length of storage time influences caking. In most cases, the t endency of a fertilizer to cake is highest during the first few weeks after produc- tion. However , if a fertilizer has a t endency to cake, in most cases prol onged storage periods will result in a significant increase in caking. Conversely, if a fertilizer does not have a ten- dency to cake, prol onged storage will usually not result in caking. The pressure exert ed at the bot t om of a stack or pile of fertilizer has a definite effect on cak- ing. As with storage time, if a fertilizer has a t endency to cake, excessive and prol onged pres- sure will result in a significant increase in caking. Under pressure, particle deformat i on may occur, resulting in increased contact area. Conversely, if a fertilizer does not have a t endency to cake, excessive and prol onged pressure (within reason- able limits) will usually not result in caking. Solutions to caking The fertilizer industry has adopt ed various mea- sures to alleviate caking, including the following: 1. The use of various drying processes to obtain a product with a low moisture content. 2. The use of various cooling processes to obtain a product with a low t emperat ure. 3. The use of various granulation, prilling, and pelletizing processes to produce larger parti- cles t hereby decreasing the surface area and number of contact points bet ween particles. 4. The use of screening equi pment to obt ai n a more uniform particle size t hereby decreasing the surface area and number of contact points bet ween particles. 5. The control of storage conditions such as RH, t emperat ure, pile height, and storage time. 6. Packaging fertilizer products in moisture- resistant bags. 7. The addition of anticaking agents (con- ditioners). As indicated, much can be done to decrease the caking t endency by improving bot h process and storage conditions. However , there is always a practical and economical limit to which the above measures can be used. Thus, in many cases the use of an anticaking agent in combina- tion with process and storage control is the obvi- ous answer to caking problems. However , it should be emphasized here that an anticaking agent cannot be used to compensat e for a poorl y pr oduced or handled fertilizer. Acti on of anticaking agents Various modes of action have been suggested to explain how anticaking agents prevent caking. The following mechanisms are commonl y cited in the literature [1, 2, 3, 4, 5, 6]: 1. Preventing saturated solutions on the surfaces of two adj acent particles from coming in contact. 102 2. Spreading of the crystallizing phase over the particle surface. 3. Nucl eat i on of small crystals during dissolu- tion / recrystallization processes. 4. Modification of crystal makeup/ behavi or dur- ing dissolution/recrystallization processes. 5. Inhibition of dissolution/recrystallization pro- cesses. 6. Creat i on of a hydrophobi c barrier on the surface of the particles. 7. Reduct i on of capillary adhesion bet ween par- ticles. 8. Dryi ng of the granule surface. 9. Reduct i on in the strength of salt bridges be- t ween particles. The mode of action that prevents caking in a particular fertilizer is det ermi ned predomi nant l y by the t ype of anticaking agent used and to a lesser ext ent the t ype of fertilizer being con- ditioned. In most cases, more than one mode of action is involved. Types of anticaking agents An anticaking agent is a material added to a fertilizer to pr omot e the mai nt enance of good physical condition (flowability) during storage and handling. Anticaking agents can be classified according to several criteria including mode of action, conditioner chemistry, met hod of appli- cation, and fertilizer type. For this discussion, anticaking agents will be assigned to two categories according to the met hod of applica- tion, namel y, (1) coating agents and (2) internal conditioners [1, 3, 4]. A fairly comprehensi ve list of commercially available anticaking agents and their producers is included in the Appendi x. Coating agents Coating agents are conditioning materials that are applied uniformly ont o t he surface of the fertilizer particles. Most coating agents are either very finely divided inert powders (dusts) that adhere to t he particle surfaces or are liquids that are sprayed ont o the surface. These anticaking agents function by various mechanisms. Inert powders such as kaolin clays (basic aluminum silicate), di at omaceous eart h/ ki esel guhr (silica), and talc (basic magnesium silicate) function as mechanical barriers bet ween particles and also serve to absorb, spread, and inactivate any solu- tion phase that may occur on particle surfaces. Wher e caking bonds do occur, the presence of dust -t ype anticaking agents usually weakens the bonds; thus, caking is less severe. Liquid coating agents usually function either as crystal modifiers to inhibit or weaken crystal growth on and be- t ween the particles or as hydrophobi c barriers to inhibit moisture absorption. Inert powders. Clay anticaking agents are ex- t remel y fine (typically 90% less than 10 jxm and 50% less than 1/ xm) and thus adhere well to the fertilizer granules. Kaolin clays are widely avail- able and relatively inexpensive. When used alone t hey are usually sufficiently effective for use on NP or NPK fertilizers and on urea. They are not normally considered effective for use on ammoni um nitrate or ot her high-nitrate prod- ucts. However , kaolin clay combi ned with cer- tain organic additives can be used with these product s; organically t reat ed kaolin is an accep- t ed condi t i oner for ammoni um nitrate. Di at omaceous earth (also referred to as kiesel- guhr) is coarser than most clays (typically 90% minus 20 txm and 50% minus 3b~m) and thus does not usually adhere to the fertilizer particles as well as clay. However , di at omaceous earth has good absorpt i on propert i es and is also an effective anticaking agent for ammoni um nitrate. The maj or disadvantages to using inert powders as anticaking agents are their diluting effect on the product analysis and their dustiness. Liquid coating agents. These agents include or- ganic surface active agents (surfactants) and non- surface active agents. Surfactants function by altering the interfacial tension bet ween a solid and a liquid. Their ac- tion as anticaking agents is not clearly under- st ood, and various mechanisms have been pro- p o s e d - p r o t e c t i o n from moisture, spreading of liquid film, modification of crystal makeup/ behavi or, inhibition of dissolution and crystalli- zation, and modification of bond tensile strength. Because surfactant molecules comprise a non- pol ar hydrophobi c (water repellent) group and one or more polar hydrophilic (having a strong affinity for water) groups, t hey can be subdivided into two classes according to their polar struc- ture: (1) ionic, which can be further classified according to the polarity of the charge carried on the active part of the molecule (anionic if the charge is negative or cationic if the charge is positive), and (2) nonionic, where the molecule is electronically neutral. The anionic surfactants commonl y empl oyed are mainly sulfonates, particularly alkyl aryl sul- fonat es obt ai ned from napht hal ene and benzene derivatives. It is primarily due to their hydropho- bic nat ure that the anionic surfactants act as anticaking agents; i. e. , this increases the contact angle of the fertilizer solution and reduces the tensile strength of the caking bond. Cationic surfactants are domi nat ed by the fatty amines, especially those with a long carbon chain-like octadecyclamine. Caking is prevent ed by t hree different mechanisms: by the formation of a hydrophobi c coating on the surface of the particles, thus improving wat er repellency; by reducing capillary adhesion bet ween particles; and by inhibiting nucleation or otherwise mod- ifying crystal growth. The largest class of nonionic surfactants is the pol yoxyet hyl ene condensates, but these have only a moder at e effect and are not widely used. Silicone fluids may be considered as nonionic surfactants; although t hey are used as anticaking agents for many powders, their use on fertilizers is limited due to their high cost. Ot her nonionic surfactants include fatty acid esters, substituted ureas, and aldehydes and ket ones with low mol ecul ar weight. Nonsurface active coating agents are organic compounds that do not exhibit surface activity but that form a moisture-resistant layer on the surface of the fertilizer particle. Typical nonsur- face active coating agents include paraffin wax, synthetic polymers, and oils. They can be used alone or in combi nat i on with an inert dust. Internal or chemical conditioners This t ype of conditioner (anticaking agent) is added to the fertilizer during processing. These conditioners act internally, usually as hardeners or crystal modifiers to improve storage prop- erties. 103 For urea conditioning, a current popul ar prac- tice in some countries is the inclusion of 0. 3%- 0. 5% of formal dehyde in the final product. The formal dehyde is added to the mol t en urea in the form of a 37% formal dehyde solution or concen- t rat ed urea-formal dehyde (UF85 containing 26% urea, 59% formal dehyde, and 15% water). For- mal dehyde addition also reduces the formation of dust in the finishing (granulation) process because the granules are harder and more resis- tant to abrasion and breakage than is unt reat ed material. For ammoni um nitrate, the most popular in- ternal condi t i oner is magnesium nitrate, which is added in the form of a solution to the molten ammoni um nitrate in many commercial pro- cesses. A t reat ed product typically contains about 1.8% magnesium nitrate [8]. Fertilizer products (diammonium phosphat e and monoammoni um phosphate) made from wet-process phosphoric acid characteristically contain significant quantities of iron and aluminum phosphat e impurities. These im- purities serve as effective internal conditioners in these products. The iron and aluminum phos- phat es are found in the products as amorphous ' gels' that harden the products and apparently immobilize the solution phase. Format i on of the iron and aluminum phosphat es under conditions of relatively high pH and low t emperat ure pro- mot es format i on of the amorphous gel-type structure rat her than the less desirable crystalline forms. Caking probl ems with some granular di ammoni um phosphat es have been traced to the use of wet-process phosphoric acid containing a low level of iron and aluminum impurities [4, 5]. Method of applying anticaking agents The met hod used to apply anticaking agents to the fertilizer depends upon the fertilizer material being t reat ed and the anticaking agent being used. The anticaking agents must always be spread u n i f o r ml y - o n the particle surface if the agent used is a coating agent or t hroughout the fertilizer if it is an internal conditioner. In certain manufacturing processes, the t reat ment is an in- trinsic part of the process, whereas in others the anticaking t reat ment may be a separat e oper- 104 ation. As ment i oned earlier, t here are a number of materials that can be used to prevent caking of fertilizers. Even so, research into new anticak- ing agents is constantly being carried out, and new product s are being devel oped and intro- duced. Devel opment is not restricted to only new product s; it includes new techniques as well. The most frequent l y used met hods for applying anticaking agents are described. Coating agents Inert powders can be supplied to the fertilizer particles by using a rot ary coating drum l ocat ed downst ream from the screening and cooling equi pment . In some cases the inert powder has been added to the fertilizer in the discharge section of a rotary cooler. This met hod is less common and generally less effective than em- ploying a separat e coating drum. The proport i on of powder applied usually is in the range of 1 %- 4 % by weight, thus reducing the analysis of t he final product . For example, urea, if coat ed with clay, will contain about 45% nitrogen in- st ead of 46%. In addition to this disadvantage, there may be difficulties in obtaining a continuous layer of coating on the granules. Despi t e these probl ems, inert powders are frequent l y used to coat granu- lar materials because this met hod is relatively simple and low in cost. Li qui d coating agents such as organic surfac- tants can be sprayed ont o the fertilizer particles as t hey pass through a rot ary coating drum. Ot her points in t he process where liquid coating agents have been added are at the end of the product cooler, on the product belt, and at bel t transfer points. The liquid coating has the fol- lowing advantages over an inert powder coating: 1. The amount of liquid coating is usually less than 0. 5%, thus resulting in smaller impact on the final product analysis; 2. It is easier to obt ai n a homogeneous coating layer with liquids than with powders; 3. There is less evolution of dust during produc- tion and handling. In some cases liquid coat- ing agents (amines, sulphonates, etc.) may also be used in combi nat i on with inert pow- ders (either added separately or the powder is pret reat ed with the liquid coating agent). Internal conditioners As previously ment i oned, formal dehyde has been used for t reat ment of urea for many years. Accordi ng to a 1982 industrial survey made by Esso Chemical, Canada, of 30 urea (solid) pro- ducers in Nort h Ameri ca, 21 producers used formal dehyde, 3 producers used URESOFT- 150, and the ot hers used a variety of ot her condition- ers or no conditioners at all (Table 1). When formal dehyde or a compound contain- ing formal dehyde is added to mol t en urea, a reaction t akes place to yield ureaforms ranging from small water-soluble molecules to moderat e- ly large water-insoluble molecules. In most com- mercial urea prilling/granulation processes, the formal dehyde addition point is either at the out- let of the second stage evaporat or where the urea concentration is above 98.5% or at the inlet of the second-stage evaporat or where the urea concent rat i on is 95% or more. Unr eact ed formal dehyde is carcinogenic and toxic to animal life. Al t hough free formal dehyde is essentially nonexistent in the product urea and t here are no known direct environmental effects resulting from the use of formal dehyde for urea t reat ment , t here is a possibility that the toxic nat ure of formal dehyde could prompt enact ment of envi ronment al prot ect i on and worker safety legislation that woul d prohibit the future use of formal dehyde for this purpose. In recognition of this possibility, TVA has done work to develop ot her conditioners for urea that could replace formal dehyde. As a result of these studies, TVA has pat ent ed an alternative process and class of conditioners for urea [9, 10]. The class of con- ditioners used is lignosulfonates with the most effective being calcium lignosulfonate. Probabl y the most popul ar internal condition- ers (stabilizing agent) used to prevent caking for ammoni um nitrate prills is magnesium nitrate. It has been used commercially for over 20 years in t he Imperial Chemical Industries, Ltd. (ICI) Nit- ram process. Al so, in the 1960s, the Agri-Chemi- cal Division of the Uni t ed States Steel Corpora- tion pat ent ed a process for adding magnesium nitrate to ammoni um nitrate melt. In 1982 A1- bright & Wilson, Lt d. , in the Uni t ed Kingdom, devel oped still anot her system for injecting mag- nesium nitrate into the ammoni um nitrate melt bef or e prilling [8]. 1 0 5 Table 1. Conditioners and storage of urea used by North Ameri can urea producers (Survey conducted by ESSO Chemical, Canada, March 1982) Response Number of producers (mailed) Number of responses Urea solution or no solid urea production Ur ea (solid) production No conditioner URESOFT-150 Clay Formal dehyde Oil-base conditioner Concentration in product Formal dehyde Clay URESOFT-150 (three responses) Maximum temperature to storage C 20 30 40 50 60 70 Addition point Type of conditioner 0. 2%- 0. 6% 3% 1. 0.004% 2. 0.05% (granules) 3. 0.025% (prills) Number of responses 2 7 12 4 2 _!1 28 Conditioner addition point Number of responses 56 42 12 30 3 3 1 21 2 URESOFT- 150 Clay Oil-base conditioner Formal dehyde Formal dehyde Time in storage 6-12 months 3- 6 months 3 months 1 week Type of product storage Bulk Bag Dehumidified storage Yes No Heat ed Dry product Dry product Dry product Dry product prills Urea melt 3 1 2 1 2o 27 Number of responses 11 3 9 2 25 27 8 35 12 12 ___2 26 106 Table 1 ( cont i nued) Number of Hei ght o f pi l e ( f t ) responses 20 or less 2 20-30 3 30-40 11 40-50 7 50-55 1 24 Screened when shi pped No 8 N H 3 Level s in storage building 120 ppm 1 10-225 ppm 1 50-250 ppm 1 100 ppm 1 25 ppm 8 12 Formal dehyde levels in storage building 2 ppm 1 0.12 ppm 1 0.06-0.09 ppm 1 0.04-0.05 ppm 1 0.029 ppm 1 0.016 ppm 1 6 Selection of anticaking agents In sel ect i ng an appr opr i at e ant i caki ng agent for a fert i l i zer, t he fol l owi ng fact ors shoul d be con- si dered: 1. Ant i caki ng effect of t he agent . 2. Avai l abi l i t y of ant i caki ng agent , its cost, and i mpact on pr oduct analysis (dosage requi red). 3. Met hod and equi pment r equi r ed for appl yi ng t he ant i caki ng agent . 4. Envi r onment al and wor ker safet y consi dera- t i ons. Al t hough t he t r end in devel oped count ri es is t o devel op and use i nt ernal -t ype ant i caki ng agent s and l i qui d coat i ng agent s, t he use of i nert powder s wi t h or wi t hout organi c additives is still c ommon in many count ri es. In eval uat i ng pot ent i al powder - t ype ant i caki ng agent s, it is advi sabl e t o first conduct an adher- ence test; powder s t hat do not adher e well when appl i ed in a wel l -desi gned coat i ng dr um are like- ly t o resul t in dust y product s and r educed an- t i caki ng efficiency. Pr oper sizing and oper at i on of t he coat i ng dr um are i mpor t ant . 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~p < < /3 e- .o *~ .~ ..= ~ ~ = < o < r..9 N u3 .'N Z < ) O Z "~ o Va ~ ~ 8 8 Ya e- o 113 < 6 "~, ~ ~ ~ o o "~ ~ = ~ . ~ -~o~ Z ~o o~.~ ~'~ cq < ==== 0 b 0 ! 0 0 ~., r~ z d e~ E .z 0 E < 0 ,s:z o r ] ? Y . e~ N 114 Re f e r e n c e s l. Using Anticaking Agents (1983) Nitrogen 146: 21-23, November-December 2. Kurshinnikov IN and Chelikidi GF (1978) Methods of Eliminating the Caking of Fertilizers. Proceedings of the Soviet-Swedish Symposium on the Beneficiation of Phosphate Rock, pp 180-186, Tallinn, Estonia 3. Rosenblom J and Zettervall S (1978) Anticaking Treat- ments of Granular Inorganic Salts Such as Phosphate Based Complex Fertilizers and Ammonium Nitrate. Proceedings of the Soviet-Swedish Symposium on the Beneficiation of Phosphate Rock, pp 158-179, Tallinn, Estonia 4. Hoffmeister G (1979) Physical Properties of Fertilizers and Methods for Measuring Them, Y-147, Tennessee Valley Authority, Muscle Shoals, Alabama 35661, USA 5. International Fertilizer Development Center (1979) Fertilizer Manual, IFDC-R-1 (also available from the United Nations Industrial Development Organization, Vienna, Austria), Muscle Shoals, Alabama 35662, USA 6. Thompson DC (1972) Fertiliser Caking and Its Preven- tion, Proceedings No. 125, The Fertiliser Society, Lon- don, United Kingdom 7. Van Hijfte WHP (1981) The Coating of Straight Nitro- gen Fertilizers. Proceedings of the 31st Annual Meeting of the Fertilizer Industry Round Table, pp 181-187, Washington DC, USA 8. Conditioning Ammonium Nitrate for Handling and Storage (1985) Nitrogen, 156: 28-34, July-August 9. Blouin GM (1986) Production of High-Strength Storage-Stable Particulate Urea, US Patent 4,587, 358. 10. Nunnelly LM and Brummitt WC TVA's Experience in Producing and Marketing Urea LS, Z-222, Tennessee Valley Authority, Muscle Shoals, Alabama 35661, USA 11. Mackay PA and Sharples KS (1985) The Use of Special Oils and Coatings to Prevent Caking of Fertilizers. Proceedings No 239, The Fertiliser Society, London, United Kingdom
SPE 90798 Solvent / Acid Blend Provides Economic Single Step Matrix Acidizing Success For Fines and Organic Damage Removal in Sandstone Reservoirs: A Niger - Delta Case Study