USRE31179E - Method of processing waste sludge from wet phosphoric acid purification facilities - Google Patents

Method of processing waste sludge from wet phosphoric acid purification facilities Download PDF

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Publication number
USRE31179E
USRE31179E US06/289,378 US28937881A USRE31179E US RE31179 E USRE31179 E US RE31179E US 28937881 A US28937881 A US 28937881A US RE31179 E USRE31179 E US RE31179E
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United States
Prior art keywords
weight
sludge
sub
slag
waste sludge
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US06/289,378
Inventor
Peter Meurer
Martin Hater
Fritz Meininghaus
Rudiger Scheel
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ThyssenKrupp Industrial Solutions AG
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Uhde GmbH
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Publication of USRE31179E publication Critical patent/USRE31179E/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B5/00Thomas phosphate; Other slag phosphates
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/902Materials removed
    • Y10S210/906Phosphorus containing
    • Y10S210/907Phosphate slimes

Definitions

  • the aim of the invention is to utilize the waste sludge from wet phosphoric acid purification facilities without causing any problems. This aim is achieved by adding the waste sludge to the steelworks slag in controlled quantities, such that the P 2 O 5 content of the mixture amounts to 3 to 9%.
  • the waste sludge is added to the warm prepared slag at a uniform rate.
  • the waste sludge is distributed uniformly over a hot slag bed.
  • the advantages attained by the invention consist primarily of the fact that a waste product from a wet phosphoric acid purification unit, said product containing a relatively high proportion of readily water-soluble and citrate-soluble P 2 O 5 as well as a relatively high proportion of compounds that would constitute unpermissible environmental pollution in that concentration, is converted by simple means to a product that is ultimately deposited on and enters the soil over a large area.
  • the other waste sludge substances thus distributed do not constitute an unpermissible pollution of the soil, since they are present in this type of fertilizer in a much lower concentration than in high-percentage phosphatic fertilizers, such as superphosphate and mixed fertilizers.
  • high-percentage phosphatic fertilizers such as superphosphate and mixed fertilizers.
  • the commonly known reason for this is that, when manufacturing high-percentage phosphatic fertilizers directly from phosphate rock or from unpurified wet phosphoric acid, the natural impurities are simultaneously introduced into the product.
  • the process according to the invention simultaneously permits the P 2 O 5 of the steelworks slag to be increased, because the content of citric-acid-soluble P 2 O 5 in the sludge is considerably higher than in the slag.
  • a reconcentration to about 3-9% P 2 O 5 by admixing waste sludge will only increase the content of residual substances to a level that is far below the permissible limits.
  • the use of waste sludge from wet phosphoric acid purification facilities represents a raw material source while obviating the necessity to use expensive phosphate rock.
  • the uniform distribution of the watery waste sludge over the hot steelworks slag constitutes a particular advantage, because this causes the residual water in the waste sludge to evaporate and the resulting mixture is thus almost dry. Expensive drying facilities are obviated to a large extent and considerable drying energy can be saved.
  • LD slag Approximately 1400 tons of LD slag and 600 tons of waste sludge are mixed in a mixing bed prior to grinding.
  • the LD slag has already been enriched to 3.5% P 2 O 5 (soluble) by admixing P 2 O 5 bearing slag.
  • the waste sludge contains 25% P 2 O 5 in the dry substance and its moisture content has been reduced to 3.5% in a pre-drying step.
  • the product obtained is a lime-based fertilizer containing 8.2% P 2 O 5 (soluble).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to a method of processing the waste sludge obtained in purification facilities for phosphoric acid produced by the wet process. The composition of this sludge is such that it cannot be utilized for any purpose in this state. It is known that sludge from wet phosphoric acid purification facilities contains different quantities of certain substances, the concentrations being such that these substances may not be allowed to mix with surface water or ground water under any circumstances, not even in the case of dumps. A typical composition of such waste sludge is as follows:
______________________________________                                    
Fe 9.0% by weight P2 O5 21.0% by weight CaO 6.2% by weight SiO2 12.5% by weight MgO 5.8% by weight Al2 O3 2.7% by weight Cr2 O3 0.7% by weight V2 O5 0.6% by weight Na2 O 18.0% by weight K2 O 0.3% by weight F 1.7% by weight C 2.5% by weight S 0.3% by weight Remainder* 18.7% by weight 100.0% by weight ______________________________________ *The remainder consists mainly of hydration water and carbonate that did not decompose at a temperature of 105° C.

Description

BACKGROUND OF THE INVENTION
The dumping of this sludge presents considerable problems. For instance, the readily water-soluble alkali-bound phosphates are washed out by rain and this will ultimately result in heavy eutrophication of the local surface water. At the same time, certain portions of the other sludge constituents are also washed out. In a wet phosphoric acid purification unit with an annular throughput of approximately 100,000 tons H3 PO4, the quantity of sludge obtained per year will be about 50,000 tons. According to the present state of engineering technology, there is no alternative but to dump this sludge. The cost of such a temporary dump is mainly determined by the land required, plastic film covering and/or lining and by the inspection requirements to ensure that the ground water is not pulluted. A final solution to the problem cannot be foreseen at present.
The aim of the invention is to utilize the waste sludge from wet phosphoric acid purification facilities without causing any problems. This aim is achieved by adding the waste sludge to the steelworks slag in controlled quantities, such that the P2 O5 content of the mixture amounts to 3 to 9%.
SUMMARY OF THE INVENTION
In an embodiment of the invention, the waste sludge is added to the warm prepared slag at a uniform rate.
In a further embodiment of the invention, the waste sludge is distributed uniformly over a hot slag bed.
The advantages attained by the invention consist primarily of the fact that a waste product from a wet phosphoric acid purification unit, said product containing a relatively high proportion of readily water-soluble and citrate-soluble P2 O5 as well as a relatively high proportion of compounds that would constitute unpermissible environmental pollution in that concentration, is converted by simple means to a product that is ultimately deposited on and enters the soil over a large area. The other waste sludge substances thus distributed do not constitute an unpermissible pollution of the soil, since they are present in this type of fertilizer in a much lower concentration than in high-percentage phosphatic fertilizers, such as superphosphate and mixed fertilizers. The commonly known reason for this is that, when manufacturing high-percentage phosphatic fertilizers directly from phosphate rock or from unpurified wet phosphoric acid, the natural impurities are simultaneously introduced into the product.
Apart from the advantages mentioned above, the process according to the invention simultaneously permits the P2 O5 of the steelworks slag to be increased, because the content of citric-acid-soluble P2 O5 in the sludge is considerably higher than in the slag. Even in the case of steelworks slag from modern converters that use oxygen blasting where the P2 O5 content of the slag has dropped to about 1%, a reconcentration to about 3-9% P2 O5 by admixing waste sludge will only increase the content of residual substances to a level that is far below the permissible limits. The use of waste sludge from wet phosphoric acid purification facilities represents a raw material source while obviating the necessity to use expensive phosphate rock.
The uniform distribution of the watery waste sludge over the hot steelworks slag constitutes a particular advantage, because this causes the residual water in the waste sludge to evaporate and the resulting mixture is thus almost dry. Expensive drying facilities are obviated to a large extent and considerable drying energy can be saved.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following numerical examples serve to describe the process according to the invention in more detail.
EXAMPLE 1
Approximately 250 tons of waste sludge are spread over an uncooled slag bed of about 300 m2 in area and containing around 1000 tons of LD steelworks slag (LD=Linz-Donawitz process). The LD slag contains 1.2% P2 O5 (soluble), while the sludge contains 21% P2 O5 (soluble) in the dry substance and 50% moisture. By virtue of the bed drying process and the subsequent turning over of the mixture, 10% of the moisture is expelled. The mixture is ground in a heater mill to a dry end product with a grain size of smaller than 0.315 mm and containing 3.4% P2 O5 (soluble).
EXAMPLE 2
Approximately 1400 tons of LD slag and 600 tons of waste sludge are mixed in a mixing bed prior to grinding. The LD slag has already been enriched to 3.5% P2 O5 (soluble) by admixing P2 O5 bearing slag. The waste sludge contains 25% P2 O5 in the dry substance and its moisture content has been reduced to 3.5% in a pre-drying step. After processing the mixture in a combined grinding and drying unit, the product obtained is a lime-based fertilizer containing 8.2% P2 O5 (soluble).
From the above examples it can be seen that while the P2 O5 content of the steelworks slag is increased, the other substances contained in the sludge are diluted. Whereas the dumping of about 50,000 t.p.a. sludge requires an area of 5000 m2, i.e. the amount of sludge per m2 is 10 tons or 10,000 kg, which fact results in an unpermissibly high pollution per m3 surface and ground water, the spreading of 25 kg/100 m2 or 0.25 kg/m2 fertilizer will produce extremely low water pollution. This means that, if the volume of the waste sludge is increased three-fold by adding steelworks sludge, the annual output of about 50,000 tons of waste sludge is distributed over an area of approximately 600 km2.

Claims (6)

We claim:
1. A method of converting a waste sludge of substantially no utility from wet phosphoric acid purification, having a relatively high, water-soluble phosphatic content and containing other environmental-polluting components, to a useful fertilizer, said method comprising contacting said sludge with steelworks slag having a relatively low phosphatic content, forming a fertilizer admixture from said sludge and slag having an averaged phosphatic content depending on the relative proportions of sludge and slag used, and reducing the concentration of said other environmental-polluting components to a non-polluting, permissible value.
2. A method according to claim 1, characterized in that waste sludge is spread fairly uniformly over a hot slag bed.
3. The method of claim 1 in which said admixture from said sludge and slag has a phosphatic content in the range of about 3% to about 9% P2 O5 by weight.
4. The method of claim 1 in which said steelworks slag is warm, and contacting said sludge and slag evaporates the water of said sludge and produces a substantially dry admixture.
5. The method of claim 1 in which said waste sludge has approximately the following composition in weight percent:
______________________________________                                    
       Fe             9.0%                                                
       P.sub.2 O.sub.5                                                    
                      21.0%                                               
       CaO            6.2%                                                
       SiO.sub.2      12.5%                                               
       MgO            5.8%                                                
       Al.sub.2 O.sub.3                                                   
                      2.7%                                                
       Cr.sub.2 O.sub.3                                                   
                      0.7%                                                
       V.sub.2 O.sub.5                                                    
                      0.6%                                                
       Na.sub.2 O     18.0%                                               
       K.sub.2 O      0.3%                                                
       F              1.7%                                                
       C              2.5%                                                
       S              0.3%                                                
       Remainder      18.7%                                               
                      100.0%                                              
______________________________________                                    
6. The method of claim 1 in which said fertilizer admixture is lime-based and its phosphatic content is substantially water-soluble.
US06/289,378 1978-12-16 1981-08-03 Method of processing waste sludge from wet phosphoric acid purification facilities Expired - Lifetime USRE31179E (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2854433A DE2854433C2 (en) 1978-12-16 1978-12-16 Process for the preparation of a P? 2? O? 5? -Containing fertilizer
DE2854433 1979-06-30

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US06/099,530 Reissue US4257898A (en) 1978-12-16 1979-12-03 Method of processing waste sludge from wet phosphoric acid purification facilities

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USRE31179E true USRE31179E (en) 1983-03-15

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US06/099,530 Ceased US4257898A (en) 1978-12-16 1979-12-03 Method of processing waste sludge from wet phosphoric acid purification facilities
US06/164,698 Expired - Lifetime US4300939A (en) 1978-12-16 1980-06-30 Method of processing waste sludge from wet phosphoric acid purification acid purification facilities
US06/289,378 Expired - Lifetime USRE31179E (en) 1978-12-16 1981-08-03 Method of processing waste sludge from wet phosphoric acid purification facilities

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US06/099,530 Ceased US4257898A (en) 1978-12-16 1979-12-03 Method of processing waste sludge from wet phosphoric acid purification facilities
US06/164,698 Expired - Lifetime US4300939A (en) 1978-12-16 1980-06-30 Method of processing waste sludge from wet phosphoric acid purification acid purification facilities

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2854433C2 (en) * 1978-12-16 1981-10-08 Uhde Gmbh, 4600 Dortmund Process for the preparation of a P? 2? O? 5? -Containing fertilizer
CA1166548A (en) * 1979-07-13 1984-05-01 Kasane Yamashita Treating agents for treating dissolved heavy metals and method of treating dissolved heavy metals with the treating agents
DE3038336A1 (en) * 1980-10-10 1982-05-27 Hoechst Ag, 6000 Frankfurt METHOD FOR PROCESSING WASTE WATER CONTAINING PHOSPHORUS
JPS62277199A (en) * 1986-05-23 1987-12-02 San:Kk Hydrophobicity imparting agent for sludge

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983594A (en) * 1956-03-22 1961-05-09 Jost Walter Trace element fertilizers
US3135595A (en) * 1962-06-13 1964-06-02 Ben F Williams Method of providing fertilizer from metal mine waste
US3579321A (en) * 1970-03-09 1971-05-18 Brandt Chem Co Inc Ammonium phosphate fertilizer composition and method
US3763041A (en) * 1971-11-24 1973-10-02 American Cyanamid Co Process of removing water from slimes
US3956119A (en) * 1974-02-19 1976-05-11 Mobil Oil Corporation Flocculation process
JPS5162557A (en) * 1974-11-27 1976-05-31 Nippon Steel Corp ARUKARISEIJUKIHAISUINO JUKIBUTSUJOKYOHOHO
US4300939A (en) * 1978-12-16 1981-11-17 Uhde Gmbh Method of processing waste sludge from wet phosphoric acid purification acid purification facilities

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983544A (en) * 1956-12-28 1961-05-09 Gen Motors Corp Finish molding for automobile bodies
US3235595A (en) * 1963-12-26 1966-02-15 Dow Chemical Co Bis[o-(2-propynyloxy)benzaldehyde] azine
US3756119A (en) * 1969-09-12 1973-09-04 Colt Ind Operating Corp Machine gun
GB1348686A (en) * 1971-06-15 1974-03-20 British Steel Corp Phosphatic fertilisers
DE2458647B2 (en) * 1974-12-09 1976-12-30 Mannesmann AG, 4000 Düsseldorf PROCESS FOR THE PRODUCTION OF BASIC, CAO-CONTAINING THINNING AGENTS

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983594A (en) * 1956-03-22 1961-05-09 Jost Walter Trace element fertilizers
US3135595A (en) * 1962-06-13 1964-06-02 Ben F Williams Method of providing fertilizer from metal mine waste
US3579321A (en) * 1970-03-09 1971-05-18 Brandt Chem Co Inc Ammonium phosphate fertilizer composition and method
US3763041A (en) * 1971-11-24 1973-10-02 American Cyanamid Co Process of removing water from slimes
US3956119A (en) * 1974-02-19 1976-05-11 Mobil Oil Corporation Flocculation process
JPS5162557A (en) * 1974-11-27 1976-05-31 Nippon Steel Corp ARUKARISEIJUKIHAISUINO JUKIBUTSUJOKYOHOHO
US4300939A (en) * 1978-12-16 1981-11-17 Uhde Gmbh Method of processing waste sludge from wet phosphoric acid purification acid purification facilities

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Publication number Publication date
DE2854433A1 (en) 1980-06-26
DE2854433C2 (en) 1981-10-08
US4257898A (en) 1981-03-24
US4300939A (en) 1981-11-17

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