CA1214020A - Production of fluid fertilizer from phosphorus furnace waste stream - Google Patents

Abstract

PRODUCTION OF FLUID FERTILIZER FROM
PHOSPHORUS FURNACE WASTE STREAM

ABSTRACT

Processes and compositions of matter are disclosed for the production of liquid fertilizers wherein wastewater from a phosphorus smelting furnace is incorporated in liquid fertilizer processes. The wastewater replaces water evapo-rated and the wastewater dissolves fertilizer salts. A serious water pollution problem is avoided when wastewater is incor-porated in liquid fertilizers. The invention discloses a process for making orthophosphate suspension fertilizer wherein impure phosphoric acid is neutralized in the condensing system, water from the condensing system is bled off, and a suspending clay is added to produce orthophosphate suspension fertilizer.
In this process, phosphorus sludge made at phosphorus furnaces is used to produce suspension fertilizer, and wastewater from phosphate smelting furnaces is recovered. New compositions of matter are disclosed. A process is disclosed for making phos-phoric acid with low impurities content wherein phosphorus sludge is burned to make impure orthophosphoric acid and the impure acid is recycled to an agglomerating step in a process for making elemental phosphorus.

Description

- - -The technical information in this appl-ication supports the following two objectivesO
Provide new processes for making liquid fertilizers wherein phosphorus-containing liquid wastes are incor-porated in fertilizer mixtures.
Produce electric furnace phosphoric acid of high purity.
My U.S. Patent ~,383,847 issued on May 17, 1983 contains much background information on energy conser-vation and waste recovery at phosphorus smelting furnacesused to produce elemental phosphorus. A liquid waste is discharged at the smelting furnaces, and the waste contains elemental phosphorus. ~erious water pollution problems result unless the waste is given extensive treat-ment to remove the elemental phosphorus. The present application focuses on use of the phosphorus-containing waste to make liquid fertilizerO The present invention provides new processes for using phosphorus sludge pro-duced at phosphorus smelting furnaces. This problem is closely related to disposal of wastewater containing elemental phosphorus.
The art of the present invention may be applied in the production of munitions wherein elemental phosphorus is the starting material Eor the production of binary nerve gas. Water wastes containing elemental phosphorus are potential pollutants at smelting furnaces. Also, water wastes are potential pollutants when the nerve gas is produced because elemental ~' '' ``~, ~?~

phosphorus must be kept under water, and water frequently is used in metering the element. The processes described herein provide envixonmentally acceptable disposal means for any of the aqueous wastes which contain elemental phosphorus, and the cost of disposal will compare favorably with other treatment methods.
Elemental phosphorus may become an important commercial product for export. The element may provide phosphorus nutrient to grow crops, and it is a source of energy when it is burned to produce phosphoric acid. Developing nations may be supplied with phosphorus nutrient and energy. One ton of elemental phosphorus provides as much nutrient as 4.~ tons of merchant-grade wet-process phosphoric acid; therefore, large savings in fuel for transportation would be realized if elemental phos-phorus is shipped instead of wet-process phosphoric acid.
Disposal of wastewater containing elemental phosphorus will seriously handicap any program to develop elemental phosphorus into an important product for export. The inevitable produc-tion of phosphorus sludge has been a serious handicap in the process for the manufacture of elemental phosphorus. The processes described in the present invention are expected tocorrect both problems.
Elemental phosphorus is produced by reacting a mixture of phosphate ore, silica rock, and reducing carbon in a smelting furnace called a submerged-arc electric furnace. The carbon combines with oxygen in the phosphate mineral releasing gaseous phosphorus. Many chemical reactions occur in the smelting furnace, and the technology is complex. The present patent , application primarily involves recovery of elemental phosphorus from the furnace gas. Nevertheless, a fuIl disclosure of the invention will require some explanation of the operation and chemistry of phosphate smelting.
The mineral in phosphate ore is fluorapatite and it is represented by the formula, CalO(PO4)6F2. However, nearly all phosphate ores contain fluorapatite in a modified form wherein carbonate ancl fluorine replace some of the phosphate radical and some of the calcium is replaced by other metals. Most commercial phosphates are mineral concentrates which contain 80 to 90 percent apatite and lO t~ 20 percent gangue material.
The mineral concentrates are prepared by beneficiating raw phosphate ore. Unbeneficiated ores are sometimes used in phosphate smelting furnaces and the percentages of apatite will be less than 80 to 90 percent because the raw ore is contami-nated with clay and silica.
The unsubstituted fluorapatite mineral contain 3.77 percent fluorine and 42.2 percent P205; its F to P205 weight ratio is 0.0~9. The F to P205 weight ratios in commercial phosphate ores may be as high as 0.14. The phosphate ores found in Tennessee and Florida are not highly substituted and they have a F to P205 weight ratio of 0.106. Unsubs-tituted fluorapatite must be heated to temperatures well ahove 2000F
before significant fluorine is volatilized. No significant quantity of fluorine would be volatilized from a phosphorus smelting furnace if unsubstituted fluorapatite is the phosphate mineral in the ore. However, specific data are not available because unsubstituted fluorapatite does not occur in commercial phosphate ores. Fluorine in substituted fluorapatite begins to volatilize at temperatures well below 2000F.

The data on the operation of phosphaie smelting furnaces are inadequate to permit precise calcuIations of the quantity of fluorine volatilized. Data from one test have shown that 9 percent of the fluorine is volatilized from the smelting furnace when the F to P205 ratio in the phosphate was 0.08.
Before the phosphate ore was calcine the F to P205 weight ratio was about 0.11; about 23 percent of fluorine was vola-tilized by calcining at about 2650F.
Operating experience has shown that volatilization of fluorine from phosphate smelting furnaces increases with the F to P205 ratio in the ore. The volatilized fluorine causes operating problems in the phosphorus condensing system because insolublP fluosilicate salts are formed in condenser water.
In the present invention processes are described to correct the condensing system operating problems when phosphate ores are smelted having a range of F to P205 weight ratios from 0.08 to 0.138~
Silica rock provides Si02 to combine with the CaO in phosphate ore to make calcium silicate slag. Phosphate ores contain some A1203, and Si02 combines with the A1203 to form calcium aluminate slag. The slag flows from the furnace as a high temperature liquid. About 18.8 percent of the electric energy input is lost in the molten slag, and this energy loss amounts to 7.7 million Btu per ton of phosphorus produced.
Energy loss is greater for unbeneficiated phosphate ores than for beneficiated phosphate ores; the unbeneficiated ores contain gangue material which increases the quantity of slag produced.
The percent P205 in the phosphate - silica rock mixture is a' measure of the energy loss in the molten slag~ Barber and Marks in Journal of Metals, December 1962, reported that a decrease of 1 percent in the P2O5 content of the phosphate-plus-silica mixture increases the electrical energy consumption about 2~5 percent. In the present invention phosphate smelting processes are disclosed wherein the P2O5 content of the phosphate-plus-silica rock mixture is increased to decrease the electric energy requirement for smelting.
Various condenser system arrangements are used to recover elemental phosphorus from furnace gas. The follow-ing two problems are common at all the production units:
Part of the condensed phosphorus is recovered asan emulsion comprised of water, solids, and discrete particles of elemental phosphorus. Recovery of the elemental phosphorus from the emulsion is costly, may be hazardous, and air and water pollution may be made worse by the recovery process.
Water inevitably comes in contact with elemental phosphorus. When this occurs, water becomes saturated with the element at a concentration of about 0.03 ppm.
Also, phosphorus becomes suspended in the water as colloidal particles. Neither dissolved phosphorus nor colloidal suspended particles are easily removed from the water. Serious water pollution problems are caused by the discharge of the contaminated water.
PRIOR A~T
Some relevant prior art is listed on the Eirst page of U.S. Patent 4,383,847 mentioned above. The following additional prior art is included.
Chemical Engineering Progress, Vol. 65, No. 6, June 1969, "Waste Effluent; Treatment and Reuse,"
J. C. Barber. The technical article gives a diagram of '~ `,~,".~

a phosphorus condensing system. A wastewater treatment method is described wherein the elemental phosphorus content oE the water is about 0.05 ppm.

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U.S. Patent 2,039,297, May 5, 1936~ "Separating Phos-Phorus," H.A. Curtis. Elemental P is separated from hot gaseous mixtures produced in P reduction furnaces by continu-ously contacting the mixtures with a solution o~ Ca(OH)2:H20 in a wt. ratio of 0.1-0.2-100 (lime:H20). The gaseous mixture which separates is principally CO saturated with H20 vapor.
Any elemental P remaining can be removed by an adsorbent. The lime H20 containing condensed P, dust particles, and precipi-tated P oxidation products are withdrawn from the bottom of the condenser and permitted to stratify. The layers of lime H20, condensed P, and sludge are separated. The sludge is dried and incorporated with a P reduction furnace charging stock. The lime H20 is recycled to the condenser with Ca(OH)2 added as needed.
U.S. Patent 2,135,486, Nov. 8, 1938, "Separating Ele-mental Phosphorus from Impurities," L. H. Almond. Elemental P is separated from a mass containing elemental P and solid impurities, such as obtained by separating dust from phos-phate reduction furnace gas or by indirect condensation of P
from phosphate reduction furnace gas. Enough H20 is rnixed with the mass to forrn a semifluid mixture. I'his mixture is fed continuously to a flash distillation zone maintained at ~750-800F. The P and H20 in the mixture are flash distilled and separated from the solid impurities continuously. The solid impurities are withdrawn from the flash distillation zone continuously.

U~S. Patent 3,084,029, April 2, 1963, "Recovery of Phosphorus from Sludge," J. C. Barber, G. H. Megar, and T. S. Sloan. Phosphorus sludge formed during the production of P by smelting phosphate rock is fed to a vessel where centrifugal force is supplied. The centrifugal force causes P globules in the sludge emulsion to coalesce to liquid P
which has a greater density than th~ impurities in the sludge.
A H20 slurry containing<~7 wt % P is removed as overflow, and a liquid underflow containing>~93 wt % P is recovered.
Treatment of the sludge with a small amount of a dispersant, such as NaOH, decreases viscosity and stickiness and thus permits the sludge to be pumped and handled more readily.
U.S. Patent 3,113,839, December 1OJ 1963, "Recovery of Phosphorus from Sludge," JO C. Barber, G. H. Megar, and T. S. Sloan. Phosphorus sludge formed during the proauction of P by smelting phosphate rock is treated by adding<~2 wt parts of NaOH/1000 wt parts oi sludge. This quantity is suffi-cient to raise the pH of the sludge from ~.3.0 to ~ 6Ø The resulting mixture is agitated for ~2-6 days and then is burned to recover P205 vapor. Alternately, the treated sludge is sub~ected to centrifugal force to recover P li~uid in the centrifuge underflow.
U.S. Patent 3,136,604, June 9, 1964, "Recovery of Phosph4rus from Sludye," J. C. Barber, G. H. Megar, and T. S. Sloa~. Phosphorus sludge formed during the production o~ P by smelting phosphate rock is treated by adding <1 wt part of ammonium lignosulfonate/1000 wt parts of sludge to reduce the viscosity. Material sufficiently caustic to rais,e the sludge pH from ~3.0 to ~6.0 is added. The resulting v~

mixture is agita*ed for ~2-6 days and burned to recover P205 vapor. Alternate'ly, the treated sludge is subjected to cen-trifugal force and'P recovered in liquid form.
U.S. Patent 3,428,430, February 18, 1969, "Method of Decreasing Sludge Formation in Phosphorus Furnace Sump,"
G. H. Megar and Arnett Hendrix. In the production of elemental P by reducing a phosphate rock blend in an electric furnace, offgases are scrubbed with sprays of H20 to condense the P
vapor. Ammonium hydroxide is usually added to the condenser H20 to maintain the pH to 5.5-6Ø The mixture is run to a condenser sump where a layer of relatively pure molten P col-lects at the bottom. Above this is a layer of sludge comprised of P droplets, solid impurities, and H20. ~bove the sludge layer at a poorly-defined boundary is a H20 layer containing P
droplets and solids in suspension. The furnace gases contain SiF4 which reacts with the condenser H20 to precipitate hydrated Si02. The precipitated Si02 occludes P and thereby promotes sludge formation. Addition of aqueous NH~F to the condenser spray H20 to maintain a F:Si atomic ratio of ~6-10:1, preferably ~6.5:1, causes formation of soluble (NH4)2SiF6 from all the SiF4, preventing formation of Si02. Less sludge is formed, and the P is easier to recover in pure form.
U.S. Patent 3,531,250, September 29, 1970, "Utilization of Phosphate Sludge as Electric Furnace Feed," Arnulf Hinz, et al.
In the usual method for the manufacture of alkali metal phos-phates from wet process H3PO4 by neutralization with NaOH a precipitate of impurities is formed. The precipitate is sepa-rated as a sludge which contains 47-53% P205, dry basis. Because of its high content of combined water, and its small particle si~e, the sludge is difficult to work up into a commercial product such as fertilizer. A method-is described for utiliz-ing the sludge for the manufacture of elemental P by mixing it with phosphate rock and drying and agglomerating the mixture by any of the usual methods. The mixture should contain less than 15% sludge, dry basis. The sludge is an effective agglom-eration agent, so other agents such as clay can be wholly or partially omitte!d. The agglomerates are stronger than usual.
U.S. Patent 3,433,601, March 18, 1969, "Separating Phosphorus from Gas Streams," H.M. Stevens. Elemental P is recovered from reduction furnace gases by cooling the mixture to a temperature below the dew point but above the melting point of P (60-180C). The P is thereby condensed in liquid form~
The liquid P is maintained in turbulent flow by recirculation to prevent sedimentation of solid impurities in the condenser and piping. Cooling is by indirect heat exchange with air or water. The method avoids the problems of "phossy water" and sludge in the usual wet method of condensing and collecting P.
U.S. Patent 3,615,218, October 26, 1971, "Recovery of Phosphorus from Electric Furnace Sludge," L.B. Post, R.E. Paul, and W. R. Crudup. During P manufacture when the P is condensed by cooling with H20, a slime containing 15-85~ P forms as a boundary layer. The emulsion of P, H20, and ~ine solids is broken by stirring at 15-45 with 3-5 wt parts CS2/part of emulsion at a Reynolds No. = (1 x 105)-(1 x 106) or a modified Reynolds No. (impeller No.) - D2Np/~ where D = diameter of the stirrer in cm, N = re~olutions/sec of the stirrer, p = density in g/cm3(1.245 for CS2), and ~= viscosity in g/cm-sec (4.956 x 10 3 for CS2?, until most of the P has dissol~ed in the CS2. Thereafter the solution is filtered and P can be recovered by distillation. The stirring time can be calcu-lated from K = (T)-(N5/6D5/3) where T = time in sec. Although stirring is ineffective when too slow, too vigorous stirring can lead to total emulsification (when K~600); K should be 100-600 when stirring for 2 min or less, 250 750 when stirring for~10 min, and 325-825 when stirring for ~16 min. In an example, a mixer with a propeller stirrer (diameter 5.4 cm) was used to stir 140 wt parts of P.slime containing ~40% P
and 250 parts CS2. Good separation was obtained by stirring for 2.5 min at 2000 rpm, 1.5 min at 8000 rpm, and 2.5 min at 8000 rpm, but total emul~ification occurred when the mixture was stirred for 5.0 min at 8000 rpm.
U.S. Patent 4,081,333, March 28, 1978, "Phosphorus Distillation," W.S. Holmes, E.J. Lowe, and E.R. srazier.
A method and apparatus are described for distilling P from P mud formed when entrained P-containing solids are scrubbed from the waste gases of a thermal P plant. A distillation fur-nace is used which has: exposed Pb in the bottom of the heating zone; an aperture ~or insertion and removal of a vessel through a substantially horizontal channel; means for closing the aperture with a vapor-tight seal; and a conduit to conduct P
vapor from the furnace to a condenser. An open thermally con-ductive vessel, or skip, containing P mud is placed in direct contact with the molten Pb at 330-620. The P is distilled from the mud as vapor and recovered. Thus, 415 kg of mud were melted in the skip and transferred when cold into the furnace containing molten Pb at 450. The furnace lid was replaced and the furnace heated to raise the contents of the skip to 600.
During 14 hr heating time 144 kg of P was recovered; 37 kg of inert material remained in the skip. Solvent extracta~le P
in the residue was <1 ppm.

.- . r V.S. Patent 3,684,461, August 15, 1972, "Phoshphorus Recovery from Aqueous Sludge," Fritz Muller, Karl-Heinz Standenbach, and Horst-Heinrich Weizenkorn. Elemental P is recovered continuously from waste H20 containing P sludge from the electrothermal production of P. The multi-step process entails filtration of the waste water using filter aids such as silicate slag, kieselguhr, or coke dust; cen-trifugation of the resulting filter cake; predrying the cake at up to 6 atm (gauge); drying and distilling the cake in multi-stages to vaporize the H20 at ~100 and then distill the P at up to 380; jointly condensing the H20 and P using filtrate, adjusted to pH 4-6 with Ca(OH)2, recovered from the initial filtration step; and removing separately the H20 and P. Residue from the drying step is discharged as a powdery, non-flammable solid. The entire process is operated in the absence of air, and drying and distillation steps being maintained under an inert atm, such as N. It is preferable to incorporate a dust separation step ahead of the condensation zone with recycle of the recovered dust to one of the preceding drying zones. The major pieces of process equipment are a centrifugal filter, a reservoir having a mixer, at least two paddle blade screw driers in series, and an injection condenser. In an e~ample employing kieselguhr as a filter aid, the filtrate contained 1 mg P/l.
and the drier residue contained P205 29.1, CaO 15.2, SiO2 40.8, F 3.7, and C 8.2%.

~4~

U.S. Patent 3,436,184, April 1, 1969, "Recovering Phosphorus from Sludge," J. A. Hinkebein. Addition of an H20-soluble inorganic hexavalent oxy-chromium compound to sludge formed in a P condenser sump causes the P to settle to the bottom in a coalesced layer. Thus, sludge decanted from a P condenser sump containing 34% liquid P, 13% solids, and 53% H20 was fed at 45 gal/hour to a mixing tank stirred with a blade rotating at 105 rpm. An aqueous 1% CrO3 solution was also fed to the tank at 90 gal/hour. The treated sludge containing 4.66% P and 89.73% H20 was con-tinuously withdrawn as overflow. Liquid P containing 0.29%
CrO3 and 0.005% benzene-insoluble matter was withdrawn from the bottom of the tank. Optionally~ the CrO3 can be added to the condenser H20.
U.S. Patent 3,515,5157, June 2, 1979, "Recovering Phosphorus from Sludge,'7 J. A. Hinkebein. The P content of sludge produced in condensing P vapor is decreased by the presence of an oxidizing agent such as CrO3 in the condenser liquor.

. ., ,, .

U.S. Patent 3,743,700, July 3, 1973, "Recovery of Phosphorus from Sludge," C. P. Orr. Phosphorus sludge obtained as a byproduct in the production of elemental P
by the electric furnace method is admixed with sufficient elemental P to provide a P:dirt ratio of at least 75:25 and continuously dried at>l00 to ~8 wt % H20. A dry, fluid sludge is produced that is readily recycled to the electric furnace.
U.S. Patent 3,852,050, December 3, 1974, "Recovery of Phosphorus," Chao Hsiao and L. B. Horton. Solids-free gas containing P4, Co, and H20, from an electric reduction furnace, is passed upward through a primary condenser where the gas is contacted countercurrently with a H20 spray at ~60 to condense a portion of the P4 as a liquid. The resulting mixture of H20 and liquid P4 is passed to a settling zone for recovery of the P4. Effluent gas from the primary condenser is then passed upward through a secondary condenser in which H20 at 4 is sprayed countercurrently down the center and along the inside walls of the condenser to quench rapidly the remaining P4 vapor into solid particles con-taining entrapped H20. The resulting slurry of solid P4 particles in H20 is fed to the settling zone for recovery as molten P4.
Proceedings of the 35th Industrial Waste Conference, Purdue ~niversity, May 13, 14, and 15, 1980, "Development of a Wastewater Management System for an Elemental Phosphorus Production Plant," John H. Koon, Gary M. Davis, Paul D. Knowlson, and Edward F. Smith, Hooker Chemicals and Plastics Corpora-tion, Columbia, Tennessee 38401. : Hooker makes elemental phosphorus and phosphoric acid at Columbia, Tennessee. Prior to the beginning of the investigation Hooker treated wastewater with lime, storage in on-site ponds, and recycle of water to process uses. The system was effective in dry weather but the ponds overflowed in wet weather. The plant is located on 110 acres of land, the rainfall is 52 inches per year, and annual evaporation is 31 inches. A program was undertaken to segregate uncontaminated storm water runoff from the plant water system, convey the combined storm water and process waste streams to storage ponds~ and to develop a treatment system capable of processing these waste streams for reuse or for discharge to a surface waterway. The following constituents were to be controlled in the plant discharge.
Total suspended solids Total phosphorus Fluoride Elemental phosphorus pH
Elemental phosphorus in wastewater varied between 50 and 350 micrograms per liter. Elemental phosphorus removal methods investigated were: chemical coagulation; alkaline hydrolysis;
air oxidation; chlorine oxidation; precoat filtration; and carbon adsorption. None showed promise with the possible excep-tion of carbob adsorption. The following treatment scheme was tried in a pilot plant.
Chemical precipitation and sedimentation employing lime and polymer addition.
GranuIar media ~iltration.
Granular activated carbon sorption.

Overall pilot-plant results are as follows.

Carbon Overall Plant Clarifier Filter column removal, water _ffluent effl_ent efflue_t Elemental phos-phorus ~g/1. 152 122 99 0.13 99.9 Phosphorus mg/l as P
Total 179 52.0 44 38 78.8 Ortho 149 18.6 14.4 13.6 88.1 Fluoride (mg/l) 157 73.7 62.6 54.8 65.1 pH 7.1 Five figures are included in the present application to aid in understanding the disclosure.
In these drawings:
Figure 1 is a diagram of a phosphorus condensing system;
Figure 2 and Figure 3 are graphs showing the solubility of ~a2SiF6 and K2SiF6/ respectively, in water and in a 15.4 percent phosphoric acid solution.
Figure 4 is a diagram illustrating the process of the invention; and Figure 5 is a diagram in which a process for making suspension fertilizer from impure phosphoric acid.
Furnace gas is shown as 1 in the Figure 1. The gas is anhydrous and it contains,about 24.9 pounds of elemental phosphorus per 1000 cubic Eeet of noncondensable gas at STP. The gas mixture is conducted through line 2 to elec-trostatlc precipitator 3. Dust is discharged at 4 at a rate of 0.07 ton per ton ~f elemental phsophorus produced.
Treated gas from the precipitator flows through pipe 5 to the bottom of an adiabatic condenser 6. Gas is saturated with water by spraying water into the gas by means of ,':~

water spray 7. Gas is cooled adiabatically from 600 to 145F. Mixture of water and liquid phosphorus flows down adiabatic condenser 6 to collecting sump 8 wherein liquid phosphorus 9 collects as a bottom layer; an emulsion of solid particles, water, and phosphorus droplets collect as layer 10; and water 11 is top layer in sump 8. Boundary between water 11 and phosphorus sludge 10 is not clearly defined. Gas leaves the adiabatic condenser through pipe 12 and enters tubular condenser 13. Water overflows a baffle in sump 8. Baffle is not shown in figure 1.
Water is recirculated from sump 8 to condenser 6 - 16a -'~ ''' ' through pipe 14. Pump 22 pumps water to spray 7. A stream of the recirculating water enters tubular condenser 13 through pipe 15 and is sprayed into tubes by spray nozzles not shown.
A stream of the recirculating water is bled off at 16 and makeup water is added at 17. The concentration o~ fluosil-cate salts in the recirculating water is kept below saturation by adding the fresh water. Gas is exhausted by pump 18 and water is added to the pump through line 19. Gas Elows to entrainment separator 20 and the c,omposition of the gas at 21 is as follows.

Percent by volume Dry W

2 0.1 0.1 CO 87.3 85.9 H2 7.9 7.7 N2 2.3 2.3 CH4 1.1 1.1 C2H2 0.6 0.6 H20 - 1.6 100.O 100.O
Pumps 23 transport phosphorus and phosphorus sludge to storage tanks through pipelines not shown.
Air leaks into the furnace gas through feed chutes and opening's in the furnace roof and gas offtake. Some of the phosphorus is oxidized by the oxygen in the inleakage forming P205. Some of the P205 is collected in the electrostatic precipitator; the remaining P205 is entrained in the gas stream and is carried into the adiabatic condenser. The P205 combines with water forming phosphoric acid.

Fluorine volatilizes from the phosphorus furnace as SiF4 and this compound combines with water in the adiabatic condenser forming fluosilicic acid, H2SiF6.
Both phosphoric and fluosilicic acids corrode steel.
It is common practice to neutralize the recirculating water at the adiabatic condenser with an alkali to control corrosion.
When either NaO~I or Na2CO3 is used to neutralize the water, sodium fluosilicate, Na2SiF6, is formed. When the concentra-tion of Na2SiF6 reaches saturatio~ the salt precipi-tates as a tenacious scale which accumulates in spray nozzles and pumps.

Consequently, water is bled from the recirculating stream at the adiabatic condenser and fresh water is added to ke~p the concentration of Na2SiF6 below saturation.
Figure 2 gives the solubility of Na2SiF6 in water and in a 15.4 percent phosphoric acid solution. Concentrations must be kept below the values shown to prevent serious operating problems from scaling of Na2SiF6. Note that Na~SiF6 is more soluble in phosphoric acid than in water, and higher concen-trations of Na2SiF6 can be tolerated in the unneutralized condenser water. However, the condensing system must be con-structed of corrosion-resistant materials if the water is unneutralized.
Sodium and potassium compounds are present in phosphate ores. Both sodium and potassium substitute for calcium in the apatite molecule. These alkali metals are constituents of clay, a substance fxe~uently used as a binder for the agglom-eration of phosphate ores. Both sodium and potassium volati-lize from the phosphorus furnace and enter the condensing system. Much of the potassium is removed from the gas stream by the electrostatic precipitator; the precipitator dust contains about 16 percent K20. Nevertheless, some potassium enters the adiabatic condenser and combines with H2SiF6 form-ing K2SiF6. The solubility of K2SiF6 in water and in 15.4 percent phosphoric acid solution is shown in figure 3. Note that K2SiF6 is much less soluble in both water and phosphoric acid than is Na2SiF6.
Ammonia is frequently used to neutralize condenser water, and ammonium fluosilicate will be formed. This salt is more soluble than either sodium or potassium fluosilicate. Problems of scale formation from the precipitation of ammonium fluo-silicate are rare. However, water must be bled from the recirculating stream to prevent scaling by Na2SiF6 and K2SiF6.
Electrostatic precipitators are not completely effective for the removal of particulates from the furnace gas. The gas entering the adiabatic condenser contains particulates which become suspended in the recirculating water. The suspended particulate concentration will increase to the point that the recirculating water will become slimy and the water spray will not effectively cool the gas by the adiabatic process.
Water must be bled from the recirculating stream to prevent such high concentrations of suspended solids. The bleedoff rate must be increased if the phosphate ore contains clay:
more sodium and potassium fluosilicate salts accumulate in the condenser water; clay contains micron size particles which become suspended in the furnace gas; and solids accumulate in the condenser water at a greater rate.
Water bled from the condensing system contains nutrients, fluorine, and elemental phosphorus as pollutants. The water is saturated with elemental phosphorus at a concentration of about 0~03 ppm. Also, the elemental phosphorus is present as colloidal particles suspended in the water as described by Isom 2~
in Journal of Water Pollution Control Federation, volume __._ _ __ _ ____ 32, No. 12, pages 1312-16 (1960). The elemen-tal phosphorus concentration should be reduced to the detection limit for analysis, or about 0.5 ppb, if the effluent is discharged as a waste. Few treatment methods are capable of reaching such low concentrations, and treatment is costly. In my U.S. Patent No. 4,383,847 mentioned above, I disclosed processes wherein the bleedoff water may be incorporated in orthophosphate fertilizer suspensions without costly treatment. The present invention discloses additional processes for incorporating the wastewater in fluid fertilizer processes.
The prior art reveals several processes for treating phosphorus sludge to recover high quality phosphorus.
In most of the processes, phosphorus is only partially separated from the solid impurities, or fuel must be burned to volatilize elemental phosphorus and water leaving a phosphorus free residue. Elemental phos-phorus is recovered by condensing the volatilized gases.
Some silicon tetra~luoride, Si~4, volatilizes ~rom the phosphorus sludge and contaminates the condensed phos-phoxus. All of the processes are too costly.
A process is disclosed in the present invention wherein phosphoric acid with low impurities content is produced from phosphorus sludge. Figure 4 is a diagram which illustrates the process~ Phosphate ore 1 and ground phosphate 2 are added to agglomerator 3. Impure ortho-phosphoric acid is added through line 16. Agglomerates 4 are anhydrous after being indurated in 3. The agglo-merated phosphate ore is smelted in 7. Reducing carbon5 and silica rock 6 are added. Phosphorus furnace gas 8 ..~ 2 ~4~2~
flows to a condensing system ~ wherein a mixture of phosphorus and phosphorus sludge 10 is recovered and pumped to a vessel 11 - 20a -, ; ~" ~
, .

for settling. High quality phosphorus is recovered by settling in 11 and is pumped through line 12 to acid unit 1~ wherein 17 is phosphoric acid product with low impurities content.
Phosphorus sludge separated in 11 is pumped through line 13 to acid unit 15 wherein orthophosphoric acid with high impuri-ties content is recycled through line 16 to the agglomerator 3.
When phosphate ores are smelted in an electric furnace, dust particles are entrained by the gases generated in the furnace. Also, some inorganic compounds are volatilized from the furnace. At some plants electrostatic precipitators are provided to remove particulates from the gas stream. However, the precipitators are not completely effective and some of the particulates remain suspended in the gas stream after treatment. The electrostatic precipitators are not designed to remove volatilized inorganic compounds, although some of these compounds condense in the precipitators and cause operating problems. Particulates and volatilized inorganic compounds are removed from the gas stream in the condensing system. The particulates collect with phosphorus particles and water to form an emulsion having a specific gravity range of about 1.3 to 1.5. Liquid elemental phosphorus has a specific gravity of 1.7. Phosphorus sludge is readily separated from liquid phosphorus by settlin~, and the liquid phosphorus layer is high purity.
Phosphoric acid is normally produced by burning the material in a stainless steel combustion chamber. A coating of polymerized phosphoric acid condenses on the inside surface of the combustion chamber and prevents the stainless steel from corroding. The phosphorus burned must be nearly anhydrous to prevent the phosphoric acid coating from hydrolyzing to , ~, 1 '~

2~

orthophosphoric acid. Humidity in air and the small amount of water entrained and dissolved in good quality phosphorus provide enough water to form polymerized phosphoric acid needed to protect the stainless steel combustion chamber.
Phosphorus sludge contains too much ~ater to burn in a stainless steel combustion chamber.
In figure 4, item 14 is an acid unit described in the publication, Industrial and Engineering Chemistry, volume 59, No. 6, June 1967, pages 18-28, "A ~igh Temperature Superphos-phoric Acid Plant," H.~. Allgood, F.E. Lancaster, Jr.,J.A. McCollum, and J.P. Simpson. The combustion chamber is constructed of A.I.S.I. Type 316 stainless steel. High quality phosphorus must be burne~ in the unit to prevent corrosion of the stainless steel.
The acid unit indicated 15 in figure 4 was described in the publication, Corrosion, volume 14, August 1958, "Corrosion Problems in the Manufacture of Phosphoric Acid from Elemental Phosphorus," J.C. Barber. The combustion chamber is con-structed of graphite blocks. High ~uality phosphorus or phosphorus sludge may be burned in the acid unit.
When the acid is recycled to the agglomerator, as disclosed in the present invention, impurities are refined in the smelting furnace and all of the product is clear phos-phoric acid with low impurities content. All of the product may be highly concentrated phosphoric acid, if this product is desired.
Eigure 5 is a diagram which discloses a process for making suspension fertilizer from the impure orthophosphoric acid. A mixture of phosphate ore, reducing carbon, and silica in 1 is smelted in furnace 2. Furnace gas 3 is treated in condensing system ~, and mixture of phosphorus and phosphorus ~z~4C~
sludge 5 is transported to settling tanks 6. Material ispumped from tanks 6 through line 7 with phosphorus sludge transported through line 8 to acid unit 10. Phosphorus sludge is burned in a combustion chamber constructed of graphite blocks, and orthophosphoric acid is produced which is recylced through line 12 to the condensing system 4 wherein acid is neutralized by ammonia from a line not shown in the diagram.
Water containing ammonium phosphate in a saturated solution and as crystallized suspension is transported through line 13 to a tank 14 equipped with an agitator not shown. A suspending clay is added to the tank by a feeder not shown in the diagram.
Orthophosphate suspension fertilizer is produced and is pumped from the tank through line 16. High quality phosphorus from settllng tanks 6 is transported through line 9 to acid unit 11.
The acid unit is equipped with a stainless steel combustion chamber. Phosphoric acid with low impurities content is removed through line 15.
A process is disclosed in figure 5 wherein both phos-phorus sludge and excess condenser water are used to make suspension fertilizer. ~ir used to burn the phosphorus sludgein acid unit 10 is adjusted so as to produce an acid mixture containing P205 and P203. Neutralization of the acid mixture with ammonia results in the formation of small sized ammonium phosphate crystals suitable for use in making suspension fertilizers. Heat generated by neutralization of orthophos-phoric acid with ammonia is removed by a tubular cooler in the condensing system.
In order that those skilled in the art may better understand how the present invention can be practiced, the following examples are given by way of illustration but not necessarily by way of limitation.

EXAMPLE I
Phosphate ore was mined in middle Tennessee and wasbeneficiated by washing, an operation which removed most of the clay. The beneficiated ore had the following dry basis analysis.
Constituent Percent P205 25.9 CaQ 36.8 Si02 22.7 Fe23 3.1 Al23 ~, o F 2.8 K20 0.8 MgO 0.3 Mn2 0 3 Na20 0.6 C2 1.5 S2 1.7 Organic C 0.2 Combined water 1.5 The F/P205 ratio in the ore was 0.108 as compared with 0.089 in fluorapatite. Analysis indicat.es moderate substitu-tion of fluorine for phosphate in the fluorapatike molecule.
The phosphate ore was agglomerated by nodulizing at a tempera-ture of 2650F. All of the C02, S02, organic C, and combined water was volatilized; 25 percent of the fluorine came off.
As a result, the P205 content of the phosphate was increased by a factor of 1.06, and the nodulized phosphate had the Eollowing composition.

Constituent Percent -P205 27~5 CaO 39 0 SiO2 24.1 2 3 3.3 A123 4.2 F 2.23 K20 0.8 MgO Ø3 10 MnO2 0.3 Na20 0.6 The F/P205 ratio was 0.081 indicating that all of the substituted fluorine and about 9 percent of the fluorapatite fluorine had been volatilized. Nodules, silica rock, and metallurgical cok~ were charged to a smelting furnace operating at a powerload of 13,400 kW. Furnace gas was treated in an electrostatic precipitator to remove suspended particulates and the gas was cooled in an adiabatic condenser by a stream of recirculating water. A 4.4 percent soda ash solution was added to the recirculating water to maintain the pH at 5.5 and prevent corrosion. The rate of soda ash addition was

3 pounds per ton of elemental phosphorus produced. A stream of water was bled off the condensing system and fresh water was added to control the concentration of suspended solids in the recirculating stream. Water was bled at a rate of 73 pounds per ton of phosphorus produced. Fluosilicates did not precipitate in the condensing system. A fluorine balance showed that 91.4 percent of the flu~rine charged was in the slag and 9.1 percent was in phosphorus sludge, making 100.5 percent accounted for. The water bled off contained about 0.16 percent fluorine and about 1.7 percent P205. Losses " :Y
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of F and P205 in the water were 0.1 pound of F per ton of elemental phosphorus and 1.2 pounds P205 per ton. The water contained about 0.4 percent suspended solids.
The water bled off was added to the first-stage ammoniator of a three-stage process for the production of orthophosphate suspension fertilizer to replace fresh water normally used to make the fertilizer. Suspension fertilizer was made at a rate of 392 pounds per ton of elemental phosphorus produced.

EXAMPLE II

Phosphate ore was mined in middle Tennessee and was beneficiated by washing as in example I. A mixture was pre-pared which comprised two parts beneficiated ore to one part unbeneficiated ore, and the mixture contained a substantial amount of clay. The mixture was briquetted wherein clay was the binder. The briquets were calcined in a nodulizing kiln as in example I but the temperature was in the range of 1865 to 2200F. In this temperature range, fluorapatite crystals begin to form and agglomerates become indurated b~ crystal interlocking. Six percent of the fluorine was volatilized during calcination. Chemical analysis of the calcined briquets was as follows.
Constituent Percent P205 26.6 CaO 37.5 SiO2 20.0 Fe23 4.1 A123 6.6 F 2.6 The F/P205 weight ratio in the calcined briquets was 0.098, indicating about half of the substituted fluorine had been volatilized.

The calcined briquets, silica rock, and metallurgical coke were charged to a smelting furnace operating at a power-load of 6580 kW. Furnace gas was treated in an electostatic precipitator to remove suspended particulates and the gas was cooled in an adiabatic condenser. The condenser water was neutralized with soda ash solution; 6 pounds of soda ash was required per ton of elemental phosphorus produced. Water was bled from the condensing s~stem at a rate of 1900 pounds per ton of elemental phosphorus re,covered. The water bled off contained about 0.28 percent fluorine. The water was added to the first-stage ammoniator of a three-stage process for the production of orthophosphate suspension fertilizer to replace fresh water. The suspension fertilizer was made at a rate of 10,800 pounds per ton of phosphorus produced.

EXAMPLE III

A mixture of Florida hard rock phosphate, silica rock, and metallurgical coke was smelted in a phosphorus furnace operating at 8050 to 8390 kW powerload. The Florida hard rock was in lump form and required no agglomeration for use in the phosphorus furnace. Analysis of the material charged to the furnace was as follows.

Constituent Percent Moisture 0.7 CaO 51.5 SiO2 2.6 Fe23 1. 1 A123 0.8 CO~ 3.2 E' 3.9 ~-!
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The F/P205 ratio was 0.109 indicating moderate substitu-tion in the Fluorapatite. The rate of fluorine volatilization during smelting was calculated to be 0.07 ton per ton of phos-phorus produced. The furnace gas was treated in an electro-static precipitator to remove suspended particulates and the gas was cooled in an adiabatic condenser. Precipitator operation with Florida hard rock was poor because deposits accumulated on the wires and frames, and these deposits were not removed by steaming or shaking the wires and frame. The deposits caused electrical grounding of the precipitator. After about a month's operation it was necessary to shut down and remove the deposits manually, at which time it was found that crystal-lized projections on the wires and frames caused the precipi-tator grounding. Composition of the deposits was as follows.

Analysis, %
Deposits on Deposit on wires in sec- second pass Constituent ond pass _ frame Ignition loss 9.6 20.4 P205 35.1 44.0 CaO 0.2 0.2 SiO2 50.1 32.2 F 0.3 0.3 K20 0.3 0.8 Fe23 0.2 4.2 Al23 0.0 o.o The crystalline material deposited in the electrostatic precipi-tator was not identified. It was anticipated that sodium fluorsilicate scale would precipitate from condenser water because the F/P205 ratio in the phosphate exceeded the ratio for fluor-apatite. Consequently, a water-cooled coil was inserted in the condenser sump and the coil was observed to determine

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whether or not fluosilicates were precipitating. Makeup water was added on the basis of observations of the coil. ~eated water was added to the gas exhauster to avoid problems of fluosilicate deposition in this unit.
The condenser water was neutralized with soda ash solu-tion, and about 438 pounds was required per ton of elemental phosphorus produced. Water was bled off at a rate of 6500 pounds per ton of phosphorus produced, and the P205 content of the water was about 0.2 percent Suspension fertilizer was produced at a rate of 37,100 pounds per ton of elemental phosphorus produced.

EXAMPLE IV
No test data were obtained when phosphoric acid solution was used instead of a neutralized solution to condense elemental phosphorus. However, data are available to calculate the results that would be obtained.
Sixty-eight percent BPL phosphate ore from Florida was agglomerated by a low-temperature process wherein orthophos-phoric acid was used to agglomerate the material; the phosphoric acid was neutralized with ground 68 BPL phosphate ore, and the agglomerates were indurated at about 300F. The composition of the ore was as follows.
Constituent Percent P205 31.1 CaO 46.6 2 3 2.59 Si2 7-3 F 3.3 The ratio of F to P205 was 0.106, and 16 percent of the fluorine was in the substituted form. Phosphate ore required to produce ....
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a ton of elemental phosphorus was about 9.5 tons and about 0.050 ton of F was volatilized from the furnace per ton of elemental phosphorus produced. The quantity of fluorine volatilized from the furnace was too large for successful operation of an electrostatic precipitator and none was used.
The calculated quantity of soda ash needed to neutralize the fluorsilicic acid in the condensing system was 92.9 pounds per ton of elemental phosphorus produced, and about 3 pounds of soda ash was needed to neutralize the phosphoric acid, making a total consumption of 95.9 pounds of soda ash per ton of phosphorus produced.
From figure 2, solubility of sodium fluosilicate is given as 0.12 pound per gallon of solution in water and 0.135 pound per gallon for 15.4 percent H3PO4. These are solubilities at 140F. Therefore, bleedoff water rate will be 6,690 pounds per ton of phosphorus when the solution is neutral and 5,430 pounds of water if a 15.4 percent H3PO4 solution is used in the condensing system. The bleedoff water was added to the first-stage ammoniator of a three-stage process for the pro-duction of orthophosphate suspension fertilizer. The suspensionfertilizer was made at a rate of 38,200 pounds per ton of phosphorus produced when the condensing water was neutralized.
When an acid solution is used for condensing, the suspension fertilizer is produced at a rate of 31,000 pounds per ton of phosphosus produced.

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EXAMPLE V
Computations similar to those in example IV were made in the present example. It was assumed that the condenser water was neutralized with KOH to form X2SiF6. Sixty-se~en pounds of KOH was required per ton of phosphorus.
Solubility of K2SiF6 is 0.036 pound per gallon in water and 0.061 pound per gallon in 15.4 percent H3PO4. The water bleedoff rate was ~4,700 pounds per ton of elemental phosphorus.
The bleedoff water was added to the first-stage ammoniator of a three-stage ammoniation process for the production of suspen sion fertilizer. The quantity of suspension fertilizer produced was 256,000 pounds per ton of phosphorus produced.

~XAMPLE VI

Computations similar to those in example IV were made in the presen~ example. It was assumed that the condenser water was neutralized with soda ash, as in example IV, and the water bleedoff rate was 6,690 pounds per ton of phosphorus when the condenser water was neutral. The bleedoff rate was 5,430 pounds when a 15.4 percent H3PO~ solution was used.
The bleedoff water was used to make a 10-30-0 base fertilizer suspension in accordance with the following formulation.

Lbs. for 1 ton Ingredientsof base suspension . _ Monoammonium phosphate fertilizer, 11-52-01,154 Anhydrous ammonia 90 Clay 30 Water 726 30Total 2,000 2~

When the condenser water was neutralized, 18,400 pounds of the base 10-30-0 suspension fertilizer was produced. When the condenser water wasa 15.4percent phosphoric acid solu-tion, 15,000 pounds of the base solution was produced.

EXAMPLE VII

Phosphate ore having a F to P205 weight ratio of 0.106 and a P205 content of 31.6 was smelted in a phosphorus furnace.
Silica rock was added to flux the mixture, and metallurgical coke was the reducing carbon. The furnace gases were treated in an adiabatically cooled condenser wherein recirculating water was neutralized to a pH of 5.5 by the addition of anhydrous ammonia. The ammonia requirement was 30 pounds per ton of elemental phosphorus produced. The water bleedoff rate was 930 pounds per ton of elemental phosphorus. The water bled off was used to make 10-30-0 base suspension fertilizer in accordance with the formulation given in example VI. The quantity of the base suspension fertilizer made was 2,560 pounds per ton of phosphorus produced.

EXAMPLE VIII

This example is similax to example VII except that phosphate ore having a F to P205 ratio of 0.11 and a P205 content of 36.2 percent was smelted. The ammonia requirement was 44 pounds per ton of phosphorus produced and the bleedoff water rate was 1,350 pounds per ton. The bleedoff water was used to make 10-30-0 base suspension fertilizer at a rate of 3,720 pounds per ton of elemental phosphorus.

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EXAMPLE IX
A mixture of phosphate ore, silica rock, and low volatile bituminous coal was smelted in a phosphorus furnace wherein the coal was reducing carbon. The coal had the following dry basis analysis.
Fixed carbon 79.4 Volatile matter 14.6 Ash 6.0~
An adiabatic condenser was used to.condense the phosphorus in the furnace gas. The condenser water contained ~0 to 125 ppm of phenol. The F to P205 weight ratio in the phosphate ore was about 0.095, condenser water was neutralized with ammonia, and water was bled off at a rate required to keep the concen-tration of ammonium fluosilicate below saturation. The bleed-off wat~r was used to make 10-30-0 base suspension fertilizer wherein the bleedoff water replaced fresh water normally added to dissolve monammonium phosphate.

EX~MPLE X

Furnace gas was treated in a condensing system illustrated in figure 1, comprising an electrostatic precipitator, an adiabatically cooled condenser, a tubular condenser, and exhausters to pump the gas. Water was bled from the condensing system to control the concentration of suspended solids in the water and to control the concentration of fluorine. The bleedoff wa-ter was combined with water from phosphorus storage tank overflow, phosphorus tank washouts, phosphorus tank car ,, , washouts, bleedoff water from phosphorus metering systems, and water from gasline washouts. Water from all these sources contained elemental phosphorus, and the water accumulated at a rate of 10,~00 pounds per ton of phosphorus produced; its suspended solids content was 3900 ppm and the elemental phos-phorus content was 1850 ppm. The contaminated water was clarified in a gravity-type clarifier wherein 92 percent of the suspended solids and 93 percent of the elemental phosphorus were recovered as phosphorus sludge. About 48 pounds of ele-mental phosphorus was recovered per ton of elemental phosphorusproduced. Clarified water contained about 130 ppm of elemental phosphorus and about 310 ppm of suspended solids. The clarified water was reused in the system, but a stream of the clarified water was bled off, mixed with cooling water, further clarified by settling in a 14-acre pond, treated with air to oxidize elemental phosphorus, and discharged as an effluent. The effluent contained 0.3 to 0.5 ppm of elemental phosphorus.
The stream of clarified water was bled off at a rate needed to control the fluorine concentration of the recirculating water at the adiabatic condenser which depended on the F to P205 ratio in the phosphate ore fed to the smelting furnace.

EXAMPLE XI

Bleedoff water from a phosphorus condenser was centri-fuged in a commercial centrifuge unit. The bleedoff water contained 1105 ppm of elemental phosphorus and the concentra-tion was reduced to 27 ppm by centrifuging. Underflow from the centrifuge contained 95.6 percent of the elemental phos-phorus in the bleedoff water.

EXAMPLE XII
Gravitational settling tests were made to clarify the water. Thirty parts per million of Purifloc* 601, a cat-ionic flocculent, and 1 part per million oE Purifloc* 501, an anionic flocculent, was added to the water. The water contained 44 ppm of elemental phosphorus before settling and the phosphorus content of supernatant liquor was 1 ppm. The supernatant liquor was clear but it was not water white.
EXAMPLE XII~
Phosphate ore was smelted in electric furnaces to produce elemental phosphorus. The furnace gas was cooled and a mixture of water, elemental phosphorus, and solid impurities was collected in sumps under the condensers.
Liquid phosphorus havin~ a higher density than the other materials settled on the bottom of the sump. Phosphorus sludge, comprised of particles of phosphorus, particles of solid impurities, and water, collected as a layer on top of the phosphorus. Condenser water collected on top of the phosphorus slude. Liquid phosphorus and phosphorus sludge were pumped daily to an empty storage tank having a capacity of 150 tons of phosphorus. Plant production rate was about 109 tons per day of elemental phosphorus.
The mixture in the storage tank was allowed to settle for approximately 24 hours. Levels of the phosphorus layer and phosphorus sludge layer were measured and samples oE
the two materials were taken and analyzed. The quantity and quality of the two materials were determined. Phos-phorus was pumped to storage by a submerged pump through a sight glass, and when phosphorus sludge appeared in the sight glass, pumping was diverted to phosphorus sludge storage. Measurements showed that 92 percent of the elemental phosphorus ~as high quality product containing 99.6 percent phosphorusO Eight percent was recovered as phosphorus sludge which varied widely in composition.

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EXAMPLE XIV

A test was made at a 15,000-kW furnace equipped with an electrostatic precipitator and an adiabatic condenser.
The purpose of the test was to compare the quality and quan-tity of phosphorus sludge with and without using the electro-statlc precipitator. For the test without a precipitator, electric current was turned off but the furnace gas continued to flow through the precipitator tubes. When the precipitator was operating, 12.2 percent of the phosphoxus produced was collected as phosphorus sludge, and the sludge contained 35.7 percent phosphorus. Without operation of the precipi-tator, 27.8 percent of the phosphorus produced was collected as sludge, but the sludge contained 52.2 percent phosphorus.
With the precipitator operating, the phosphorus contained 98.8 percent of elemental phosphorus; without the precipitator operating, the phosphorus contained 96.4 percent elemental phosphorus. Smelting of phosphate ore with a high F/P205 ratio will preclude operation of electrostatic precipitators because crystallized deposits accumulate on the frames and wires and cause electric grounding. Larger amounts of phos-phorus sludge must be processed if precipitators are not used.

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EXAMPLE XV
Phosphorus separated from phosphorus sludge by settling was burned in a stainless steel phosphoric acid unit to pro-duce concentrated acid of high purity. Following is an analysis in percent by weight.

Percent Constituent by weight P205 79 g Fe 0.001 Al ~0.001 Cr None found Ni 0.001 Mo None found As 0.001 Pb 0.0002 SiO2 0.001 CaO 0.004 F 0.01 C1 None found S 0.002 The metal/P205 ratio was 95 x 10 6, and the F/P205 ratio was 125 x 10 6. The high quality phosphoric acid can be used in making animal feed supplements and in preparing other high quality phosphate chemicals. Also, highly concentrated phos-phoric acid was produced which had the P205 distributed among various species of phosphoric acids as shown below.
Percent Ortho 17.5 Pyro 40.1 Tripoly 22.1 Tetrapoly11.5 Pentapoly5.6 Hexapoly 2.1 Heptapoly1.2 ~ ~J~4 EXAMPLE X~I
Phosphorus was produced at a smelting furnace wherein 8 percent of the elemental phosphorus was in the phosphorus sludge and 92 percent was in the high ~uality phosphorus. The phosphorus sludge was comprised of 80 percent elemental phos-phorus and 20 percent benzene-insoluble impurities on a dry basis. The benzene-insoluble impurities had the following composition.
Percent CaO 9 SiO2 7 Fe23 6 C (by difference) 20 Total 100 The phosphorus sludge was burned in a combustion chamber. The combustion chamber was a graphite electrode which had been bored out. The hydrator was a graphite block chamber, and a stainless steel venturi scrubber removed particulates rom the gases. Phosphoric acids produced in the combustion chamber, hydrator, and venturi scrubber were combined, and the concen-tration o~ the combined acid was 53 percent P205. The acid contained -the following percentages of impurities.

Percent F 0.1 CaO 0.5 Si2 0 4 Fe23 0.3 A123 0.2 C 1.
Total impurities 2.6 The water used to hydrate the P205 to form acid was clarified condenser water. The quantity was 340 pounds per ton of eIemental phosphorus produced.
The impure phosphoric acid produced from phosphorus sludge was used to agglomerate phosphate ore in accordance with the following formulation.
330 parts 68~ BPL phosphate ore 42 parts ground phosphate 63 parts impure phosphoric,acid produced from phosphorus sludge 85 parts water Approximately 4,000 pounds of water per ton of phosphorus was re~uired to agglomerate the phosphate ore. Clarified condenser water can be used to provide the agglomerating water. Impure acid produced from phosphorus sludge was therefore recycled to the phosphorus furnace.

EXAMPLE XVII

Phosphorus sludge was processed in a phosphoric acid production unit wherein the sludge was injected into a horizontal chamber called a vaporizer. Sufficient air was put into the vaporizer -to burn about 20 percent of the elemental phosphorus.
The remainder of the elemental phosphorus and the water were vaporized; they flowed to a vertical combustion chamber through a duct. Additional air was put in the combustion chamber to burn the phosphorus. The gases were hydrated by water sprays in another vertical chamber. The gases were conducted to a venturi scrubber by means of a duct. Phosphoric acid was recovered in the combustion chamber, hydrator, and venturl scrubber. The combined acid contained 58 percent P205 and 3 percent P203.

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The phosphoric acid mixture was used to make diammonium phosphate fertilizer by the vacuum crystallization method.
Much of the P203 in the phosphoric acid remained dissol~ed in the mother liquor and the concentration of P203 exceeded 3 percent. Excessive nucleation of diammonium phosphate crys-tals occurred. A crystal slurry was obtained which could not be centrifuged because of the fineness and gelatinous character of the solids. The crystal slurry had properties desired for the preparation of suspension fertilizers. When the P203 concentration of the mother liquor was in the range of 1.5 to 3 percent and about 8 percent of SO4 ions were present, the diammonium phosphate crystals were larger and thicker and they had properties desired f~r diammonium phosphate as crystal fertilizer.
EXAMPLE XVIII
In this example a process is described for treating phosphorus-containing waste at a plant which converts elemental phosphorus into other phosphorus chemicals. However, the total process has not been carried out as described.
Elemental phosphorus was received in tank cars and pumped to storage tanks. A layer of water was kept over the phosphorus to prevent it from burning. Phosphorus was pumped to metering tanks for processing into the chemicals. Water displac'ed phosphorus in the metering tanks; water rate was measured and its rate was controlled in order to measure and control the phosphorus feed rate.
When water comes in contact with elemental phosphorus the water becomes saturated with the element, and colloidal ~
particles of phosphorus become suspended. The water was reused ~ ~- r~

in a closed system, but fresh makeup water was added at a rate needed to keep the maximum concentration of elemental phosphorus at 100 ppm. Water was bled from the system as make-up water was added. The water bled from the system was treated with a flocculent and clarified by settling. The elemental phosphorus content of the supernatant water was less than 1 ppm and it was returned ~o the recirculating water system. Underflow from the settling operation was used to prepare a 10-30-0 base suspension fertilizer wherein ammonia, solid ammonium phosphate fertilizer, and the underflow were mixed to dissolve the monoammonium phosphate. A precipitate formed from impurities in the monoammonium phosphate, and a suspending clay was added to keep the precipitate in suspension.

EXAMPLE XIX

The integrated process described below has not been carried out, but technical data were obtained on most of the steps comprising the process.
A mixture of phosphate ore, silica rock, and reducing carbon was smelted in an electric furnace. The furnace gas was treated in a condensing system wherein most of the elemental phosphorus was recovered in an adiabatic condenser. A mixture of liquid phosphorus and phosphorus sludge was pumped to a settling tank to separate the two materials. The phosphorus sludge was converted to orthophosphoric acid in a production unit comprised of a vaporizer, graphite combustion chamher, carbon block hydrator, and a stainless steel venturi scrubber.
The product was a mixture of phosphoric and phosphorous acids;
the mixture contained 53 percent P205 and 3 percent P203.

In addition, the acid contained 1.5 percent inorganic impuri-ties and 1.1 percent carbon. The acid was black; it was added to the condenser water and this water was neutralized to a pH of about 6 by ammonia. Small sized ammonium phosphate crystals precipitated in the recirulating water and were suspended by the turbulence in the recirculating water. A
stream of the recirculating water was bled off and pumped to a tank equipped with an agitator. Prior to filling the tank a gelled clay was put in. 'rhe mixture was agitated and pumped to storage for sale as a suspension f~rtilizer.
Liquid phosphorus separated from the phosphorus sludge was converted to highly concentrated phosphoric acid with low impurities content. The metals/P205 ratio in the acid was about 70 x 10 6, and the F/P205 ratio was about 130 x 10 6.

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Claims (21)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the production of fluid fertilizer comprising the steps of:
(a) smelting a mixture of phosphate ore, reducing carbon, and silica rock in a submerged-arc electric furnace wherein a phosphorus-containing gas is evolved;
(b) treating phosphorus-containing gas in an electro-static precipitator to remove suspended dust;
(c) cooling the phosphorus-containing gas in an adiabatic condenser wherein water is sprayed into the condenser, collected in a sump, and recirculated to the condenser;
(d) adding an alkaline material to the recirculating stream of water to maintain the pH in the range of 5.5 to 6.0;
(e) adding fresh water to the recirculating stream;
(f) bleeding off a stream of water from the recirculating stream;
(g) clarifying bleedoff water from step (f);
(h) adding clarified bleedoff water from step (g) to an orthophosphate suspension fertilizer process comprised of three stages of ammoniation wherein clarified bleedoff water is added to the first-stage ammoniator.

2. A process for the production of fluid fertilizers as in claim 1 wherein clarified bleedoff water from step (g) is added to an orthophosphate suspension fertilizer process comprised of two stages of ammoniation wherein clarified bleedoff water is added to the first-stage ammoniator.

3. A process for the production of fluid fertilizers as in claim 1 wherein clarified bleedoff water from step (g) dissolves monoammonium phosphate to produce a base suspension fluid fertilizer.

4. A process for the production of fluid fertilizers as in claim 1 wherein clarified bleedoff water from step (g) dissolves diammonium phosphate to produce a base suspension fluid fertilizer.

5. A process for the production of fluid fertilizers as in claim 1 wherein precipitator dust from step (b) is added to an orthophosphate suspension fertilizer process comprised of three stages of ammoniation wherein the precipitator dust is added to the first-stage ammoniator.

6. A process for the production of fluid fertilizers as in claim 1 wherein bleedoff water in step (f) is clarified in step (g) by centrifuging.

7. A process for the production of fluid fertilizers as in claim 1 wherein bleedoff water in step (f) is clarified in step (g) by treating the water with a flocculent and removing the suspended solids by gravitational settling.

8. A process for the production of fluid fertilizers as in claim 1 wherein ammonia is added in step (d) to maintain the pH in the range of 5.5 to 6Ø

9. A process for the production of fluid fertilizers as in claim 1 wherein alkaline potassium compounds are added in step (d) to maintain the pH in the range of 5.5 to 6Ø

10. A process for the production of fluid fertilizers as in claim 1 wherein phosphoric acid is added to the recircu-lating stream of water in step (d).

11. A process for the production of -fluid fertilizers as in claim 1 wherein the F/P205 weight ratio of the fluorapatite in the phosphate ore in step (a) is in the range of 0.080 to 0.095.

12. A process for the production of fluid fertilizers as in claim 1 wherein the reducing carbon in step (a) is low volatile matter content bituminous coal.

13. A process for the production of phosphoric acid wherein:
(a) a mixture of phosphate ore, phosphoric acid, and ground phosphate is agglomerated by tumbling;
(b) agglomerates in step (a) are indurated in the temperature range of 220° to 1500°F;
(c) indurated agglomerates in step (b) are mixed with reducing carbon and silica rock;
(d) mixture in step (c) is smelted in a submerged-arc electric furnace wherein a phosphorus-containing gas is evolved;
(e) phosphorus-containing gas in step (d) is cooled in an adiabatic condenser wherein water is sprayed into the condenser, collected in a sump; and recirculated to the condenser;
(f) phosphorus-containing wastewater is added to the recirculating stream;
(g) a stream of water is bled off;
(h) phosphorus and phosphorus sludge condensed in the adiabatic condenser is separated by gravitational settling;
(i) phosphorus sludge in step (h) is burned in a graphite combustion chamber;

(j) gases from combustion chamber in step (i) are contacted with bleedoff water from step (g) in a hydrator constructed of carbon blocks;
(k) gases from hydrator in step (j) are treated in a venturi scrubber;
(l) phosphoric acid collected in combustion chamber, hydrator, and venturi scrubber is recycled to step (a);
(m) liquid phosphorus separated in step (h) is processed into phosphoric acid in a stainless steel production unit;
(n) phosphoric acid produced in step (m) is processed into phosphate chemicals.

14. A process for the production of phosphoric acid as in claim 13 wherein the F/P205 weight ratio of the fluor-apatite in the phosphate ore in step (a) is in the range of 0.095 to 0.140.

15. A process for the production of phosphoric acid as in claim 13 wherein the graphite combustion chamber in step (i) is made from a solid, cylindrical piece of graphite.

16. A process for the production of phosphoric acid as in claim 13 wherein the reducing carbon in step (c) is low volatile matter content bituminous coal.

17. A process for the production of phosphoric acid as in claim 13 wherein a mixture of phosphate ore, phosphoric acid, and ammonia is agglomerated by tumbling in step (a) and in step (b) agglomerates are indurated in the temperature range of 220° to 300°F.

18. A process for the production of fluid fertilizer comprising the steps of:

(a) smelting a mixture of phosphate ore, reducing carbon, and silica rock in a submerged-arc electric furnace wherein a phosphorus-containing gas is evolved;
(b) cooling the phosphorus-containing gas in an adiabatic condenser wherein an aqueous slurry is sprayed into the condenser, collected in a sump, and recirulated to the condenser;
(c) adding ammonia to the recirculating slurry at the adiabatic condenser;
(d) cooling the phosphorus-containing gas in a tubular condenser;
(e) transporting phosphorus and phosphorus sludge to a vessel for separation of phosphorus and phos-phorus sludge by gravitational settling;
(f) processing phosphorus sludge into an acid mixture comprised of phosphoric and phosphorous acids;
(g) recycling mixture of acids in step (f) to step (b) wherein acids are neutralized with ammonia in step (c);
(h) bleeding off a stream of neutralized slurry in step (b);
(i) mixing slurry bled off in (h) with monoammonium phosphate, ammonia, and suspending clay to produce a base suspension fluid fertilizer;
(j) processing liquid phosphorus in step (e) into phosphoric acid in a stainless steel production unit;

19. A process for the production of phosphoric acid as in claim 18 wherein the F/P205 weight ratio of the fluorapa-tite in the phosphate ore in step (a) is in the range of 0.08 to 0.140.

20. A process for the production of phosphoric acid as in claim 18 wherein phosphorus-containing wastewater is flocculated and clarified by gravitational settling and super-natant water is added in step (f).

21. A composition of agglomerated phosphate ore and silica rock mixture having a Si02/.Ca0 weight ratio of 0.85 wherein the P205 content of the mixture is in the range of 26 to 32 percent.