US3800466A - Composition for treating aqueous alkaline fuel - Google Patents

Composition for treating aqueous alkaline fuel Download PDF

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Publication number
US3800466A
US3800466A US00207270A US3800466DA US3800466A US 3800466 A US3800466 A US 3800466A US 00207270 A US00207270 A US 00207270A US 3800466D A US3800466D A US 3800466DA US 3800466 A US3800466 A US 3800466A
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catalyst metal
fuel
additive
aqueous
fuel additive
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US00207270A
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A Heit
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Lanxess Sybron Chemicals Inc
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Sybron Corp
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Assigned to SYBRON CHEMICALS INC., A DE CORP. reassignment SYBRON CHEMICALS INC., A DE CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SYBRON CORPORATION
Assigned to FIRST NATIONAL BANK OF BOSTON, THE reassignment FIRST NATIONAL BANK OF BOSTON, THE SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SYBRON CHEMICAL INDUSTRIES INC.
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
    • F28G9/00—Cleaning by flushing or washing, e.g. with chemical solvents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/12—Combustion of pulp liquors

Definitions

  • An additive consisting of a water soluble salt of manganese, copper, iron, tin, nickel or cobalt or mixtures of these metals is solubilized in an aqueous medium at an alkaline pH with a conventional sequestering agent and added to the aqueous fuel in proportions of about 2 to about 50ppm based on the metal ion.
  • the additive is stable and soluble in the aqueous fuel. Oxygen demand of slag is substantially reduced and slag is softer and more friable.
  • the present invention relates to compositions of matter and process for the combustion-of aqueous alkaline fuel to improve the burning characteristics and reduce the adverse effects of combustion products on the structures with which they come in contact. More particularly the invention is concerned with the combustion of aqueous alkaline fuels in recovery boilers in paper making processes.
  • the production of pulp from wood by the Kraft process is practiced on aworld-wide scale.
  • the process yields ahigh strength pulp suitable for many of the heavier applications of paper products, e.g. sturdy cartons, bags, wrappings-and the like.
  • the process consists in the digest-ion of wood' chips, primarily conifers, ina water solution of sodium hydroxide and sodium sulfide under heat and pressure sothat substantialdelignihfi cation: takes place along withsome loss of cellulose and other sugar polymers. The resulting.
  • black liquor solution-and a portion of the washings from the pulp recovery constitutes the so called weak blackliquor which is then subjected to concentration by flash evaporation until the total solid content has reached 55' too-5* percent,-which after concentration is referred to as black liquor.
  • the black liquor has sufficient calorific value to support combustion and isthusdirected into the recovery boilers wherethe useful heat derived from combustion is applied to the evaporation of the weak black liqour.
  • Another objective of this operation is the recovery of sodium carbonate and sodium sulfide,-both of which emerge at the base of the recovery boiler as amolten stream which is taken up in water, subsequently treated with calcium hydroxide to yield the so called white liquorfor the digestion of fresh'charges of wood chips.
  • the recovery boilersemployed in the combustionof the black liquor are frequently beset by fouling problems due to aconstant flow upwards past the super heaters and economizersof the boiler apparatus of dust laden flue gas.
  • the bulk of the of the flue dust is-trapped on the surface of highvoltageelectrodes and removed andredissolved in the black liquor for subsequentreprocessing.
  • a significant fraction of the flue gas however,-deposits on the super heaters and economizer of the boiler.
  • These deposits can develope to a thickness which impedes heat-transfer as well as the free movement of the combustiongases to the stack.
  • the process of the build-up of such deposits is referred to herein as slagging and the deposits themselves are referred to as slag. This is not to be confused with the smelt which comprises the fused chemicals recovered at the bottom of the recovery boiler.
  • soot blowing procedures such as, discharge of super heated steam against the affected surfaces, or mechanical actions such as manual tamping of the sections where slag build-up has occurred. Regardless of these procedures however, shutdown of the whole recovery boiler plant is necessitated periodically in order to remove the accumulated slag.
  • lt' isanother object of this invention to provide an additive which is solublized in the aqueous alkaline fuel so that it is effectively present during combustion of the fuel.
  • Another object of this invention is to provide an additive' which substantially reduces the total oxygen demand of the by-products of combustion in the flue gas so that slag deposited on boiler parts is more friable and more readily removed.
  • FIGURE represents graphically the reduction of a total oxygendemand of particulate matter borne in the flue gas of a l(raft" process recovery boiler plotted over a period of time.
  • the novel additive composition of this invention is formed from a water soluble salt of a catalyst metal selected from the group'consisting of manganese, copper, iron, tin, nickel, cobalt and mixtures thereof.
  • the sequestering agent employed in the additive of this invention is not critical and any conventional sequestering agent is employed with good results.
  • the additive is dissolved in water and maintained at an alkaline pH in order to insure activation of the sequestering agent prior to use in the invention.
  • the solubilized additive is preferably premixed with the aqueous alkaline fuel just prior to its injection into the combustion zone.
  • the amount of additive utilized may vary depending upon the composition of the aqueous alkaline fuel, as will be discussed hereinafter, however, good results are achieved when the additive is metered at the rate of between about 5 ppm and 50 ppm of catalyst metal ion.
  • particulate matter derived from flue gases in the burning of black liquor in the Kraft paper making process indicates that the principal components of the particulate matter are sodium carbonate, sodium sulfate, sodium sulfide, carbon, water soluble organic matter, insoluble matter (primarily calcium carbonate, calcium clays and iron oxide) and sodium chloride. It is believed that the slag which accumulates on the boiler surfaces is difficult to remove because of its low fusion temperature and a natural internal cohesive strength due to bonding properties of associated organic materials. Substantial reduction or elimination of sodium sulfide, elemental carbon and soluble organic matter will result in a particulate composition which has a higher fusion point and is more friable.
  • Elimination or substantial reduction of these three undesirable elements of the particulate composition is most readily effected by oxidation in view of the nature of the combustion process involved.
  • the introduction of additional oxygen into the combustion zone is impractical and undesirable, particularly in a black liquor recovery boiler in view of the fact that oxygen has a tendency to adversely effect the sulfidity of material coming off the primary burning zone in the recovery boiler unit.
  • Sulfidity is that portion of the sodium ions present as sodium sulfide, which is one of the chemicals recovered in the smelt.
  • variable valence such as copper, manganese, iron, nickel and cobalt are known to be oxidation catalysts and have been used to promote improved burning in fossil fuels.
  • metal elements of variable valence such as copper, manganese, iron, nickel and cobalt are known to be oxidation catalysts and have been used to promote improved burning in fossil fuels.
  • the use of these catalysts in aqueous alkaline fuels has been restricted due to the fact that these metals are generally insoluble under conditions encountered in the fuels.
  • the present invention provides an additive in which catalyst metal ions selected from the group consisting of maganese, copper, iron, tin, nickel and cobalt or mixtures thereof, are provided in a form which they are stable and soluble under alkaline conditions and more particularly are soluble in the presence of conditions of alkalinity and sulfidity encountered in the black liquor of the Kraft process.
  • the catalyst metal ions are provided from their water soluble salts such as acetate, sulfate, chloride, bromide, iodide and the like.
  • the additive of this invention can employ a single species or a mixture of species of catalyst metal ions with equally good results.
  • the catalyst metal ions are sequestered prior to their introduction into the aqueous alkaline fuels.
  • Conventional sequestering (chelating) agents are used such as for example; polyamines, such as ethylene diamine, triethylene tetraamine; hydroxy polycarboxylic acids, such as, tartaric, malic, citric and the like; and N subsituted carboxylic acids, such as ethylene diamine tetraacetic acid and nitrilotriacetic acid.
  • chelating or sequestering agents are by way of example only and it should be understood that other conventional chelating or sequestering agents may be used with equal effectiveness.
  • the additive of this invention when solublized and ready for use is essentially an aqueous alkaline solution of the catalyst metal ion and a sequestering agent, although minor amounts of other ingredients, such as an antioxidant, may also be included to improve stability or shelf life of the solubilized additive.
  • the catalyst metal ion is supplied from the water soluble salt of the catalyst metal ion such as the acetate, sulfate, iodide, bromide, chloride and the like.
  • the solublized additive which has a pH preferably on the order of 9 to 10, is alkaline in order to initiate the sequestering action of the sequestering agent.
  • the total proportions of the ingredients in the additive are not critical, except set forth below, although it is preferred to maintain the total solids content of the additive between about 25% to about 55% in order to avoid phase separation problems such as may occur if the solubilized additive is subjected to low temperatures.
  • the total proportions of the additive are not critical, the relative proportion of catalyst metal ion to sequestering agent is important in maintaining stability of the addtive.
  • the additive of this invention Due to the catalytic effect of the additive of this invention, relatively minor amounts are effective in improving the friability and removability of slag formed during the combustion of aqueous alkaline fuels.
  • the additive is effective in amounts as low as 2 parts per million based on catalyst metal although the results are improved with increasing amounts of catalyst metal in the fuel.
  • the presence of an excess amount of additive in the fuel is not detrimental although in the interest of economy it is preferred that the additive be present in concentrations of about to 50 ppm, based on catalyst metal.
  • EXAMPLE I The following formulation were prepared and tested for solubility-stability in aqueous alkaline fuels.
  • Sodium sulfite is present as an antioxidant.
  • Formula B of Example I was field tested in an 800 ton recovery unit operating in a paper mill using the kraft sulfate process. Particulate flue gas samples were taken during the operation of the recovery unit from a duct between the economizers section and cyclone of the recovery unit. Formula B additive was continuously added to the black liquor in the salt cake mixing tank of the recovery unit at the rate of 100-120 ppm of additive (about 2 ppm based on catalyst metal ion) per million parts of black liquor. A sample was taken prior to treatment in accordance with this invention, and at twenty four hour periods thereafter for 4 days. Each sample of particulate matter was tested for carbon content, soluble organic content and sodium sulfide content.
  • Total oxygen demand of the sample which is a convenient measure of activity of the additive of this invention is defined and determined as follows:
  • Total oxygen demand is the sum of the oxygen required to oxidize carbon to carbon dioxide, the amount of oxygen to oxidize sodium sulfide to sodium sulfate and the oxygen demand of the water soluble organics.
  • the oxygen demand of carbon is determined by multiplying percent carbon by 32/12 while the oxygen demand for sodium sulfide is determined by multiplying percent sodium sulfide by 64/78.
  • the reduction in total oxygen demand is due to the presence of the catalyst metal which, by virtue of the additive of this invention, is present in effective amounts in the combustion zone because the additive is solubilized in the black liquor fuel.
  • the addtive is employed in economical amounts as distinguished from the prior art attempts to slurry catalyst metal oxides in the black liquor which required uneconomical amounts of metal oxide powders because of losses due to the insolubility of the powders in the black liquors. There was no adverse effect on the sulfidity balance of the recovery process indicating that the increased oxidation of carbon, sodium sulfide, and water soluble organics in the flue gas was not determental to the recovery process.
  • An aqueous alkaline fuel additive to reduce the detrimental effects of slagging encountered in the com- 25 bustion of alkaline aqueous fuel comprising an alkaline aqueous solution of a catalyst metal ion and a sequestering agent in sufficient quantity to maintain said catalyst metal ion in solution in an alkaline aqueous fuel, said catalyst metal being selected from the group consisting of manganese, copper, iron, tin, nickel, cobalt and mixtures thereof.
  • aqueous fuel additive of claim 1 having a total solids content of between about 25% to about 55%.
  • the fuel additive of claim 1 consisting essentially Manganeous acetate 5.82% Sodium hydroxide 10.00% Tartaric acid 15.75% Water 68.24%
  • the fuel additive of claim 1 consisting essentially of:
  • An alkaline aqueous fuel composition comprising a substantially uniform blend of a major amount of an alkaline aqueous fuel yielding upon combustion carbon and water soluble organics and a minor but effective amount, of a sequestered catalyst metal selected from the group consisting of manganese, copper, iron, tin, nickel, cobalt and mixtures'thereof.
  • the fuel composition of claim 13 comprising from about 2 ppm to about 50 ppm of said catalyst metal.
  • aqueous fuel composition of claim 13 comprising at least the stoichiometric amount of sequestering agent to sequester said catalyst metal ion for maintaining said catalyst metal ion in solution.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Making Paper Articles (AREA)
  • Catalysts (AREA)
  • Paper (AREA)
US00207270A 1971-12-13 1971-12-13 Composition for treating aqueous alkaline fuel Expired - Lifetime US3800466A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US20727071A 1971-12-13 1971-12-13

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US3800466A true US3800466A (en) 1974-04-02

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US (1) US3800466A (enExample)
JP (1) JPS4864202A (enExample)
AR (1) AR195091A1 (enExample)
AT (1) AT325940B (enExample)
BR (1) BR7208225D0 (enExample)
CA (1) CA962059A (enExample)
DE (1) DE2257279A1 (enExample)
FI (1) FI55066C (enExample)
FR (1) FR2163541B1 (enExample)
GB (1) GB1367563A (enExample)
IL (1) IL40652A (enExample)
NO (1) NO132055C (enExample)
SE (1) SE407092B (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287090A (en) * 1979-07-30 1981-09-01 Pfefferle William C Method of treating flue deposits and composition therefor
US4514256A (en) * 1983-04-18 1985-04-30 Kober Alfred E Method of minimizing slagging in the burning of black liquid
US4968324A (en) * 1988-06-13 1990-11-06 Deutsche Bp Ag Process for producing a solid, finely divided fuel based on coal
US5740745A (en) * 1996-09-20 1998-04-21 Nalco Fuel Tech Process for increasing the effectiveness of slag control chemicals for black liquor recovery and other combustion units
US5900112A (en) * 1995-04-03 1999-05-04 North Carolina State University Method of reducing the viscosity of a black liquor using thiocyanate salt
US20120276648A1 (en) * 2011-04-29 2012-11-01 Schlumberger Technology Corporation Electrostatically stabilized metal sulfide nanoparticles for colorimetric measurement of hydrogen sulfide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE417114B (sv) * 1977-07-25 1981-02-23 Mo Och Domsjoe Ab Forfarande for forebyggande av inkrustbildning i cellulosafabriker

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US896876A (en) * 1908-06-22 1908-08-25 Coal Treating Company Process for controlling the combustion of fuel.
US2610112A (en) * 1949-11-16 1952-09-09 Universal Oil Prod Co Soot removal compositions
US2801168A (en) * 1949-04-02 1957-07-30 Goddard Harold Oliver Waste sulphite liquor recovery
US2845338A (en) * 1953-10-15 1958-07-29 Nat Aluminate Corp Fuel additive for removing and inhibiting fireside deposits

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US896876A (en) * 1908-06-22 1908-08-25 Coal Treating Company Process for controlling the combustion of fuel.
US2801168A (en) * 1949-04-02 1957-07-30 Goddard Harold Oliver Waste sulphite liquor recovery
US2610112A (en) * 1949-11-16 1952-09-09 Universal Oil Prod Co Soot removal compositions
US2845338A (en) * 1953-10-15 1958-07-29 Nat Aluminate Corp Fuel additive for removing and inhibiting fireside deposits

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287090A (en) * 1979-07-30 1981-09-01 Pfefferle William C Method of treating flue deposits and composition therefor
US4514256A (en) * 1983-04-18 1985-04-30 Kober Alfred E Method of minimizing slagging in the burning of black liquid
US4968324A (en) * 1988-06-13 1990-11-06 Deutsche Bp Ag Process for producing a solid, finely divided fuel based on coal
US5900112A (en) * 1995-04-03 1999-05-04 North Carolina State University Method of reducing the viscosity of a black liquor using thiocyanate salt
US5740745A (en) * 1996-09-20 1998-04-21 Nalco Fuel Tech Process for increasing the effectiveness of slag control chemicals for black liquor recovery and other combustion units
US5894806A (en) * 1996-09-20 1999-04-20 Fuel Tech, Inc. Process for increasing the effectiveness of slag and/or corrosion control chemicals for combustion units
US20120276648A1 (en) * 2011-04-29 2012-11-01 Schlumberger Technology Corporation Electrostatically stabilized metal sulfide nanoparticles for colorimetric measurement of hydrogen sulfide

Also Published As

Publication number Publication date
AU4897872A (en) 1974-05-23
SE407092B (sv) 1979-03-12
NO132055B (enExample) 1975-06-02
IL40652A0 (en) 1972-12-29
NO132055C (enExample) 1975-09-10
CA962059A (en) 1975-02-04
AT325940B (de) 1975-11-10
AR195091A1 (es) 1973-09-10
FI55066B (fi) 1979-01-31
JPS4864202A (enExample) 1973-09-06
ATA1048072A (de) 1975-01-15
FR2163541B1 (enExample) 1976-08-20
GB1367563A (en) 1974-09-18
FR2163541A1 (enExample) 1973-07-27
DE2257279A1 (de) 1973-06-28
IL40652A (en) 1975-05-22
BR7208225D0 (pt) 1973-08-23
FI55066C (fi) 1979-05-10

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AS Assignment

Owner name: SYBRON CHEMICALS INC., BIRMINGHAM ROAD, BIRMINGHAM

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SYBRON CORPORATION;REEL/FRAME:004345/0022

Effective date: 19841211

AS Assignment

Owner name: FIRST NATIONAL BANK OF BOSTON, THE

Free format text: SECURITY INTEREST;ASSIGNOR:SYBRON CHEMICAL INDUSTRIES INC.;REEL/FRAME:004756/0206

Effective date: 19870724