WO1995009041A1 - Acid emission reduction - Google Patents

Acid emission reduction Download PDF

Info

Publication number
WO1995009041A1
WO1995009041A1 PCT/CA1994/000537 CA9400537W WO9509041A1 WO 1995009041 A1 WO1995009041 A1 WO 1995009041A1 CA 9400537 W CA9400537 W CA 9400537W WO 9509041 A1 WO9509041 A1 WO 9509041A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquor
alkaline earth
earth metal
compound
flue gas
Prior art date
Application number
PCT/CA1994/000537
Other languages
French (fr)
Inventor
Klaus Oehr
Original Assignee
Dynamotive Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dynamotive Corporation filed Critical Dynamotive Corporation
Priority to SK429-96A priority Critical patent/SK42996A3/en
Priority to BR9407727A priority patent/BR9407727A/en
Priority to AU77373/94A priority patent/AU677436B2/en
Priority to KR1019960701633A priority patent/KR960704617A/en
Priority to DE69411931T priority patent/DE69411931T2/en
Priority to DK94928240T priority patent/DK0721367T3/en
Priority to JP7510028A priority patent/JPH09505768A/en
Priority to EP94928240A priority patent/EP0721367B1/en
Publication of WO1995009041A1 publication Critical patent/WO1995009041A1/en
Priority to LVP-96-134A priority patent/LV11533B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/38—Removing components of undefined structure
    • B01D53/40—Acidic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides

Definitions

  • ACID EMISSION REDUCTION FIELD OF THE INVENTION This invention relates to a method of reducing acid emission from a flue, a liquor additive to inject into a flue gas to reduce acid emission and a method of producing the liquor.
  • Acid rain is a problem throughout the world. Acid rain affects the environment by reducing air quality, rendering lakes acid and killing vegetation, particularly trees. It has been the subject of international dispute. Canada and the United States have argued over the production of acid rain. Britain and Scandinavia are other antagonists.
  • the sulphur dioxide typically originates from the combustion of a sulphur containing fuel, for example coal.
  • the sulphur dioxide is oxidised in the atmosphere to sulphur trioxide and the trioxide is dissolved to form sulphuric acid.
  • the rain is thus made acid.
  • the oxides of nitrogen also are a factor in producing acid in the atmosphere.
  • the emission of oxides of nitrogen in the United States and Canada is about one fifth sulphur dioxide emissions. But that still means that millions of tons of oxides of nitrogen are fed to the atmosphere each year.
  • Planners for electrical utilities in particular are developing strategies for reducing emissions of sulphur dioxide and nitrogen oxides in the production of electrical and thermal power.
  • the majority of fossil fuel used in power production contains sulphur which produces sulphur dioxide and hydrogen sulphide during combustion.
  • Gas desulphurization systems are known. The majority rely on simple basic compounds such as calcium carbonate, sodium carbonate and calcium hydroxide to react with the acidic sulphur containing species to produce non-volatile products such as calcium sulphite, calcium sulphate and sodium sulphate. Urea and ammonia have been used to react with oxides of nitrogen generated during fossil fuel combustion to produce non-toxic nitrogen gas but urea and ammonia are expensive.
  • aqueous alkali metal acetates for example aqueous calcium acetate, calcium magnesium acetate and barium acetate
  • carbon combustion accelerators and calcium oxide precursors but cost effective calcium desulphurization and combustion accelerator agents have not yet been found.
  • Production of nitrogen oxides during fossil fuel combustion increases with combustion temperature and residence time. Increasing the combustion rate or decreasing the combustion temperature of fossil fuels decreases nitrogen oxide emissions but the prior art has not revealed how this can be achieved.
  • Unite States Patent 4,615,871 to Yoon describes the reduction of the sulphur content of flue gas derived from combustion of a sulphur containing fuel.
  • An aqueous solution containing an alkaline earth metal formate or acetate is sprayed into the flue gas. This process requires the expensive production of pure solutions of calcium formate and calcium acetate. As the solutions are not contacted with the sulphur containing fuel they cannot enhance fuel combustion rates to reduce nitrogen oxide emissions.
  • the present invention seeks to produce a method of reducing acid emission from a flue, a liquor useful in flue gas combustion and a method of producing that liquor, all of which avoid the prior art problems.
  • the present invention is a method of reducing acid emission from a flue gas produced by combustion of a sulphur - containing fuel, the method comprising introducing into a flue containing the flue gas, a pyrolysis liquor containing a thermolabile alkaline earth metal compound able to decompose at flue gas temperature to produce an alkaline compound able to react with sulphur dioxide.
  • the pyrolysis liquor is incorporated into the fuel but the pyrolysis liquor containing the thermolabile compound may be injected into the flue.
  • the fuel may be, for example, coal, petroleum tar or pitch.
  • the pyrolysis liquor is derived from a feed stock containing cellulose, lignin or starch.
  • the pyrolysis liquor is usually acidic and is at least partially neutralized by a basic alkaline earth metal compound.
  • the acidic components of the pyrolysis liquor typically carboxylic acids, and the basic alkaline earth metal compound, react to produce the thermolabile compound.
  • the basic compound may be an alkaline earth metal oxide, hydroxide of carbonate. Calcium carbonate is preferred for cheapness and availability.
  • Oxidation can oxidize carbonyl species contained in the pyrolysis liquor, for example aldehyde, to a carboxylic acid, able to react with the alkaline earth metal compound.
  • a desirable oxidizing agent is oxygen, typically introduced by aeration of the at least partially neutralized pyrolysis liquor.
  • the invention provides a liquor additive to inject into a flue gas resulting from the combustion of a sulphur containing fuel to reduce the acid content of the flue gas, the liquor comprising a pyrolysis liquor, initially acidic, at least partially neutralized by a basic alkaline earth metal compound, whereby the liquor contains at least one thermolabile alkaline earth metal compound able to decompose at flue gas temperature to produce an alkaline compound able to react with sulphur dioxide.
  • the invention is a method of producing a liquor containing at least one thermolabile compound, able to decompose at the temperature of a flue gas to produce alkaline compounds able to react with sulphur dioxide in the flue gas, the method comprising at least partially neutralizing an acidic pyrolysis liquor with a basic alkaline earth metal compound.
  • the simple alkaline earth metal compounds that are added to pyrolysis liquor act with various carboxylic acids present in the liquor to produce, for example, carboxylates, phenoxides, saccharides and the like. All these alkaline earth metal organic compounds undergo thermal decomposition to yield carbonates, bicarbonates, hydroxides and oxides on heating over a wide range of temperatures after the treated pyrolysis liquor has been mixed with a sulphur- containing fuel.
  • Thermal decomposition of the organic salts produces higher surface area calcium oxide than has been achieved from non-organic metal salts, such as calcium carbonate. It is believed that this is due to the abrasive and turbulent action of gases such as carbon dioxide and water generated during the thermal decomposition. The effect is particularly useful for rupturing sulphite and sulphate films fouling the oxide adsorbents, such as calcium oxide, used in sulphur dioxide removal during fossil fuel combustion. Furthermore the moles of gas evolved per mole of alkali earth metal oxide, hydroxide or carbonate during thermal decomposition of the alkaline earth metal salts derived from biomass pyrolysis liquors, is much higher than the amount of gas produced from conventional sources. The following equations illustrate this fact:
  • Sulphur containing fuels which are hydrophobic in nature have a greater ability to absorb alkali metal salts from pyrolysis liquors, which have a hydrophobic as well as hydrophilic component, unlike conventional aqueous solutions of alkaline earth carboxylate salts, such as calcium acetate and calcium formate, which only have a hydrophilic component.
  • Deacidification of the biomass pyrolysis liquor with alkaline earth metal salts increases its fuel value by reducing or eliminating the corrosive nature of the liquor.
  • the combination of alkaline earth metal salts with biomass pyrolysis liquor represents a relatively inexpensive source of alkaline earth containing additive for reducing sulphur dioxide and nitrogen oxide during sulphur-containing fuel combustion or gasification.
  • An alkaline earth salt liquor e.g. calcium carbonate
  • an acidic biomass pyrolysis liquor e.g. calcium carbonate
  • solutions e.g. organic hydrophobic solution plus aqueous hydrophilic solution
  • suspension of alkaline earth salts e.g. calcium propionate, calcium glycolate, calcium formate, calcium acetate, calcium lactate, calcium phenoxides, calcium saccharides, etc.
  • Pyrolysis liquor is aerated in the presence of alkaline earth metal compounds such as carbonates, hydroxides, or oxides to oxidize or disproportionate some or all of the carbonyl species contained in the pyrolysis liquors, such as aldehydes, to carboxylic acid species which can form salts such as those described in Example 1.
  • alkaline earth metal compounds such as carbonates, hydroxides, or oxides to oxidize or disproportionate some or all of the carbonyl species contained in the pyrolysis liquors, such as aldehydes, to carboxylic acid species which can form salts such as those described in Example 1.
  • alkaline earth metal compounds such as carbonates, hydroxides, or oxides to oxidize or disproportionate some or all of the carbonyl species contained in the pyrolysis liquors, such as aldehydes, to carboxylic acid species which can form salts such as those described in Example 1.
  • Biomass pyrolysis liquor is mixed with alkaline earth metal compounds(s) in the presence of sulphur containing fossil fuel such as powdered coal, with or without aeration, prior to combustion or gasification.
  • the purpose of this approach is to increase alkaline earth compound adsorption or decomposition of acidic surface coal species or those contained in the pyrolysis liquor.
  • the biomass pyrolysis liquor mixed with alkaline earth metal compounds, as described in Example 3 may be injected directly into the flue, subsequent to the combustion, to achieve the desired neutralization.
  • the only requirement is that the flue gas be hot enough to cause the breakdown of the organic compounds into simple basic inorganic compounds able to neutralize the sulphur compounds.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Catalysts (AREA)
  • Control And Other Processes For Unpacking Of Materials (AREA)
  • Gasification And Melting Of Waste (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Cold Cathode And The Manufacture (AREA)
  • Saccharide Compounds (AREA)
  • Fats And Perfumes (AREA)
  • Industrial Gases (AREA)

Abstract

A method of reducing acid emission from a flue gas produced by combustion of a sulphur - containing fuel. A pyrolysis liquor containing a thermolabile alkaline earth metal compound is introduced into a flue containing the flue gas. The alkaline earth metal compound is able to decompose at flue gas temperature to produce an alkaline compound able to react with sulphur dioxide in the flue gas. A liquor additive to inject into a flue gas resulting from a combustion of a sulphur containing fuel to reduce the acid content of the flue gas is also described. The liquor comprises a pyrolysis liquor, initially acidic but at least partially neutralized by basic alkaline earth metal compounds. The resulting liquor contains at least one thermolabile alkaline earth metal compound able to decompose at flue gas temperature to produce an alkaline compound able to react with sulphur dioxide. A method of producing the liquor is also described.

Description

ACID EMISSION REDUCTION FIELD OF THE INVENTION This invention relates to a method of reducing acid emission from a flue, a liquor additive to inject into a flue gas to reduce acid emission and a method of producing the liquor.
DESCRIPTION OF THE PRIOR ART Acid rain is a problem throughout the world. Acid rain affects the environment by reducing air quality, rendering lakes acid and killing vegetation, particularly trees. It has been the subject of international dispute. Canada and the United States have argued over the production of acid rain. Britain and Scandinavia are other antagonists.
In the main acid rain stems from sulphur dioxide produced in smoke stacks. The sulphur dioxide typically originates from the combustion of a sulphur containing fuel, for example coal. The sulphur dioxide is oxidised in the atmosphere to sulphur trioxide and the trioxide is dissolved to form sulphuric acid. The rain is thus made acid. The oxides of nitrogen also are a factor in producing acid in the atmosphere. The emission of oxides of nitrogen in the United States and Canada is about one fifth sulphur dioxide emissions. But that still means that millions of tons of oxides of nitrogen are fed to the atmosphere each year. Although it is believed that the production of sulphur dioxide has stabilized, larger emissions of the oxides of nitrogen are anticipated because of the increased use of fossil fuels.
With the passage of the International Clean Air Act amendments, such as issued in the United States in 1990, the curbing of acid emissions has become a priority. Planners for electrical utilities in particular are developing strategies for reducing emissions of sulphur dioxide and nitrogen oxides in the production of electrical and thermal power. The majority of fossil fuel used in power production contains sulphur which produces sulphur dioxide and hydrogen sulphide during combustion.
Gas desulphurization systems are known. The majority rely on simple basic compounds such as calcium carbonate, sodium carbonate and calcium hydroxide to react with the acidic sulphur containing species to produce non-volatile products such as calcium sulphite, calcium sulphate and sodium sulphate. Urea and ammonia have been used to react with oxides of nitrogen generated during fossil fuel combustion to produce non-toxic nitrogen gas but urea and ammonia are expensive.
Conventional alkaline adsorbents such as calcium carbonate and calcium hydroxide undergo thermal decomposition to calcium oxide at high temperature which reacts readily with the sulphur dioxide. However, the adsorbents suffer from fouling problems. Calcium sulphite or calcium sulphate is formed at the surface of the calcium oxide particles. This results in substantial amounts of unreacted, alkaline calcium oxide being produced during flue gas desulphurization. These alkaline solid wastes are toxic and undesirable. Successful attempts to solve this problem have relied on particle abrasion achieved in fluidized bed combustion of fossil fuels. For example in the combustion of coal, calcium sulphite/sulphate surfaces can be partially ruptured to expose fresh calcium oxide substrate, which can undergo further reaction with the sulphur species.
The prior art has also described the use of aqueous alkali metal acetates, for example aqueous calcium acetate, calcium magnesium acetate and barium acetate, to act as carbon combustion accelerators and calcium oxide precursors but cost effective calcium desulphurization and combustion accelerator agents have not yet been found. Production of nitrogen oxides during fossil fuel combustion increases with combustion temperature and residence time. Increasing the combustion rate or decreasing the combustion temperature of fossil fuels decreases nitrogen oxide emissions but the prior art has not revealed how this can be achieved.
Unite States Patent 4,615,871 to Yoon describes the reduction of the sulphur content of flue gas derived from combustion of a sulphur containing fuel. An aqueous solution containing an alkaline earth metal formate or acetate is sprayed into the flue gas. This process requires the expensive production of pure solutions of calcium formate and calcium acetate. As the solutions are not contacted with the sulphur containing fuel they cannot enhance fuel combustion rates to reduce nitrogen oxide emissions.
Techniques for the rapid pyrolysis of lignocellulosic - or starch - containing waste biomass to produce fuels with a high calorific value have been described. These fuels are acidic and corrosive to combustion equipment due to their high carboxylic acid content. The fuel value of such liquors is limited by this acidity.
It is known that aqueous solutions of calcium acetate can be used to improve the speed of coal gasification.
RELEVANT LITERATURE
Shanpei Ye, and Zhenzong Fu, "Desulfurization Test of Sorbent El in a Bench-Scale Fluidized-Bed Coal
Combustor", Coal Combustion Science and Technology of Industrial and Utility Applications, Hemisphere Publishing Corporation, New York, pages 565-572 teach particle to particle abrasion in fluidized beds of fossil fuels.
Levendis, 1989, "Catalysis of the Combustion of Synthetic Char Particles by Various Forms of Calcium Additives", Journal of Energy and Fuel discusses the use of aqueous alkali metal acetates as combustion accelerators.
Elliot et al., 1990-1991, "Energy and Fuels", Volume 5, pages 399 to 410; Beckman, D., and Graham, R., "Economic Assessment of a Wood Fast Pyrolysis Plant", AITBC Conference, Interlaken, Switzerland 1992; Piskorz J., et al., "Liquid Products from the Fast Pyrolysis of Wood and Cellulose", Research in Thermal Biomass Conversion, Elsevier Science Publishers, New York, 1988, pages 557 to 571, all relate to the rapid pyrolysis of biomass to produce fuels.
Ohtsuka, Yasuo and Tomita, Akira, 1991, "Catalytic Gasification of Low-Rank Coals with Calcium Acetate", and "Calcium Magnesium Acetate, An Emerging Bulk Chemical for Environmental Applications", Elsevier Science Publishers, New York, pages 253 to 271, discuss use of calcium acetate in coal gasification.
SUMMARY OF THE INVENTION The present invention seeks to produce a method of reducing acid emission from a flue, a liquor useful in flue gas combustion and a method of producing that liquor, all of which avoid the prior art problems.
Accordingly, and in a first aspect, the present invention is a method of reducing acid emission from a flue gas produced by combustion of a sulphur - containing fuel, the method comprising introducing into a flue containing the flue gas, a pyrolysis liquor containing a thermolabile alkaline earth metal compound able to decompose at flue gas temperature to produce an alkaline compound able to react with sulphur dioxide.
Preferably the pyrolysis liquor is incorporated into the fuel but the pyrolysis liquor containing the thermolabile compound may be injected into the flue.
The fuel may be, for example, coal, petroleum tar or pitch.
In a preferred embodiment the pyrolysis liquor is derived from a feed stock containing cellulose, lignin or starch. The pyrolysis liquor is usually acidic and is at least partially neutralized by a basic alkaline earth metal compound. The acidic components of the pyrolysis liquor, typically carboxylic acids, and the basic alkaline earth metal compound, react to produce the thermolabile compound.
The basic compound may be an alkaline earth metal oxide, hydroxide of carbonate. Calcium carbonate is preferred for cheapness and availability.
It may be desirable to oxidize the at least partially neutralized pyrolysis liquor. Oxidation can oxidize carbonyl species contained in the pyrolysis liquor, for example aldehyde, to a carboxylic acid, able to react with the alkaline earth metal compound. A desirable oxidizing agent is oxygen, typically introduced by aeration of the at least partially neutralized pyrolysis liquor.
In a further aspect the invention provides a liquor additive to inject into a flue gas resulting from the combustion of a sulphur containing fuel to reduce the acid content of the flue gas, the liquor comprising a pyrolysis liquor, initially acidic, at least partially neutralized by a basic alkaline earth metal compound, whereby the liquor contains at least one thermolabile alkaline earth metal compound able to decompose at flue gas temperature to produce an alkaline compound able to react with sulphur dioxide.
In yet a further aspect the invention is a method of producing a liquor containing at least one thermolabile compound, able to decompose at the temperature of a flue gas to produce alkaline compounds able to react with sulphur dioxide in the flue gas, the method comprising at least partially neutralizing an acidic pyrolysis liquor with a basic alkaline earth metal compound.
In the invention the simple alkaline earth metal compounds that are added to pyrolysis liquor act with various carboxylic acids present in the liquor to produce, for example, carboxylates, phenoxides, saccharides and the like. All these alkaline earth metal organic compounds undergo thermal decomposition to yield carbonates, bicarbonates, hydroxides and oxides on heating over a wide range of temperatures after the treated pyrolysis liquor has been mixed with a sulphur- containing fuel.
Thermal decomposition of the organic salts, for example calcium salts, produces higher surface area calcium oxide than has been achieved from non-organic metal salts, such as calcium carbonate. It is believed that this is due to the abrasive and turbulent action of gases such as carbon dioxide and water generated during the thermal decomposition. The effect is particularly useful for rupturing sulphite and sulphate films fouling the oxide adsorbents, such as calcium oxide, used in sulphur dioxide removal during fossil fuel combustion. Furthermore the moles of gas evolved per mole of alkali earth metal oxide, hydroxide or carbonate during thermal decomposition of the alkaline earth metal salts derived from biomass pyrolysis liquors, is much higher than the amount of gas produced from conventional sources. The following equations illustrate this fact:
Calcium carbonate. Only 1 mole of gas evolved per mole of calcium oxide generated
CaC03 ■* CaO + C02
Calcium glycolate 5 Moles of gas evolved per mole of metal oxide generated
Ca(HO-CH2-COO)2 + h 02 → CaO + 2C02 + 3H20 In the absence of oxygen (e.g. gasification), calcium oxide or other species can still be generated with the evolution of gas by reactions such as the following: Calcium acetate
Ca(CH3COO)2 -» CaO + CH3-CO-CH3 + C02 acetone
Sulphur containing fuels which are hydrophobic in nature have a greater ability to absorb alkali metal salts from pyrolysis liquors, which have a hydrophobic as well as hydrophilic component, unlike conventional aqueous solutions of alkaline earth carboxylate salts, such as calcium acetate and calcium formate, which only have a hydrophilic component.
Absorption of hydrophobic plus hydrophilic alkaline earth metal salts such as those derived from calcium will increase the speed of coal combustion thereby reducing nitrogen oxide emissions.
Deacidification of the biomass pyrolysis liquor with alkaline earth metal salts increases its fuel value by reducing or eliminating the corrosive nature of the liquor. The combination of alkaline earth metal salts with biomass pyrolysis liquor represents a relatively inexpensive source of alkaline earth containing additive for reducing sulphur dioxide and nitrogen oxide during sulphur-containing fuel combustion or gasification.
The following examples describe the invention:
Example 1
Preparation of Alkaline Earth Salt Liquors
An alkaline earth salt liquor (e.g. calcium carbonate) is mixed with an acidic biomass pyrolysis liquor to produce a hydrophobic/hydrophilic solution, or solutions (e.g. organic hydrophobic solution plus aqueous hydrophilic solution) or suspension of alkaline earth salts (e.g. calcium propionate, calcium glycolate, calcium formate, calcium acetate, calcium lactate, calcium phenoxides, calcium saccharides, etc.).
Example 2
Preparation of Alkaline Earth Salt Liquors
Pyrolysis liquor is aerated in the presence of alkaline earth metal compounds such as carbonates, hydroxides, or oxides to oxidize or disproportionate some or all of the carbonyl species contained in the pyrolysis liquors, such as aldehydes, to carboxylic acid species which can form salts such as those described in Example 1. Examples of these oxidation and disproportionation products could include the following:
Formaldehyde -* formic acid Hydroxyacetaldehyde • * glycolic acid Methyl glyoxal -* pyruvic acid Aromatic aldehydes -» phenols or aromatic carboxylic acids Example 3
Preparation of Alkaline Earth Salt Liquors in the
Presence of Fossil fuels
Biomass pyrolysis liquor is mixed with alkaline earth metal compounds(s) in the presence of sulphur containing fossil fuel such as powdered coal, with or without aeration, prior to combustion or gasification. The purpose of this approach is to increase alkaline earth compound adsorption or decomposition of acidic surface coal species or those contained in the pyrolysis liquor.
Example 4
In addition to the above procedure, the biomass pyrolysis liquor mixed with alkaline earth metal compounds, as described in Example 3, may be injected directly into the flue, subsequent to the combustion, to achieve the desired neutralization. The only requirement is that the flue gas be hot enough to cause the breakdown of the organic compounds into simple basic inorganic compounds able to neutralize the sulphur compounds.
Although the forgoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be readily apparent to those of ordinary skill in the art in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the appended claims.

Claims

I CLAIM:
1. A method of reducing acid emission from a flue gas produced by combustion of a sulphur - containing fuel, the method comprising introducing into a flue containing the flue gas, a pyrolysis liquor containing a thermolabile alkaline earth metal compound able to decompose at flue gas temperature to produce an alkaline compound able to react with sulphur dioxide.
2. A method as claimed in claim 1 in which the pyrolysis liquor is incorporated into the fuel.
3. A method as claimed in claim 1 in which the pyrolysis liquor containing the thermolabile alkaline compound is injected into the flue.
4. A method as claimed in claim 1 in which the fuel is coal, petroleum tar or pitch.
5. A method as claimed in claim 1 in which the pyrolysis liquor is derived from a feed-stock containing cellulose, lignin or starch.
6. A method as claimed in claim 5 in which the pyrolysis liquor is acidic and is at least partially neutralized by a basic alkaline earth metal compound, the liquor and the alkaline earth metal compound reacting to produce the thermolabile compound.
7. A method as claimed in claim 6 in which the basic compound is an alkaline earth metal oxide, hydroxide or carbonate.
8. A method as claimed in claim 7 in which the basic compound is calcium carbonate.
9. A method as claimed in claim 1 including oxidizing the alkaline pyrolysis liquor prior to introducing it into the flue.
10. A method as claimed in claim 9 in which the oxidation is by air.
11. A liquor additive to inject into a flue gas resulting from the combustion of a sulphur containing fuel to reduce the acid content of the flue gas, the liquor comprising a pyrolysis liquor, initially acidic, at least partially neutralized by a basic alkaline earth metal compound, whereby the liquor contains at least one thermolabile alkaline earth metal compound able to decompose at flue gas temperature to produce an alkaline compound able to react with sulphur dioxide.
12. A liquid as claimed in claim 11 in which the pyrolysis liquor is derived from a feed-stock containing cellulose, lignin or starch.
13. A liquor as claimed in claim 11 in which the basic alkaline earth metal compound is an alkaline earth metal oxide, hydroxide or carbonate.
14. A liquor as claimed in claim 13 in which the basic alkaline earth metal compound is calcium carbonate.
15. A method of producing a liquor containing at least one thermolabile compound, able to decompose at the temperature of a flue gas to produce alkaline compounds able to react with sulphur dioxide in the flue gas, the method comprising at least partially neutralizing an acidic pyrolysis liquor with a basic alkaline earth metal compound.
16. A method as claimed in claim 15 in which the basic compound is an alkaline earth metal oxide, hydroxide or carbonate.
17. A method as claimed in claim 16 in which the basic compound is calcium.
18. A method as claimed in claim 15 including oxidizing the alkaline pyrolysis liquor.
19. A method as claimed in claim 18 in which the oxidation is carried out with air.
PCT/CA1994/000537 1993-09-30 1994-09-27 Acid emission reduction WO1995009041A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
SK429-96A SK42996A3 (en) 1993-09-30 1994-09-27 Acid emission reduction, liquid additive and method of its producing
BR9407727A BR9407727A (en) 1993-09-30 1994-09-27 Reduction of acid emission
AU77373/94A AU677436B2 (en) 1993-09-30 1994-09-27 Acid emission reduction
KR1019960701633A KR960704617A (en) 1993-09-30 1994-09-27 ACID EMISSION REDUCTION
DE69411931T DE69411931T2 (en) 1993-09-30 1994-09-27 REDUCTION OF ACID EMISSIONS
DK94928240T DK0721367T3 (en) 1993-09-30 1994-09-27 Acid emission reduction
JP7510028A JPH09505768A (en) 1993-09-30 1994-09-27 Reduced acid emissions
EP94928240A EP0721367B1 (en) 1993-09-30 1994-09-27 Acid emission reduction
LVP-96-134A LV11533B (en) 1993-09-30 1996-04-30 Acid emission reduction

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/130,123 1993-09-30
US08130123 US5458803B1 (en) 1993-09-30 1993-09-30 Acid emission reduction

Publications (1)

Publication Number Publication Date
WO1995009041A1 true WO1995009041A1 (en) 1995-04-06

Family

ID=22443155

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1994/000537 WO1995009041A1 (en) 1993-09-30 1994-09-27 Acid emission reduction

Country Status (20)

Country Link
US (2) US5458803B1 (en)
EP (1) EP0721367B1 (en)
JP (1) JPH09505768A (en)
KR (1) KR960704617A (en)
CN (1) CN1068242C (en)
AT (1) ATE168580T1 (en)
AU (1) AU677436B2 (en)
BR (1) BR9407727A (en)
CA (1) CA2172846A1 (en)
CZ (1) CZ92296A3 (en)
DE (1) DE69411931T2 (en)
DK (1) DK0721367T3 (en)
ES (1) ES2122331T3 (en)
LV (1) LV11533B (en)
NZ (1) NZ273900A (en)
PL (1) PL313764A1 (en)
SI (1) SI9420056A (en)
SK (1) SK42996A3 (en)
TW (1) TW320569B (en)
WO (1) WO1995009041A1 (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5458803B1 (en) * 1993-09-30 1999-08-03 Dynamotive Corp Acid emission reduction
ZA959926B (en) * 1995-11-03 1997-02-20 Dynamotive Corp Reduction of acid rain and ozone depletion precursors.
US5817282A (en) * 1996-03-28 1998-10-06 Dynamotive Technologies Corporation Reduction of nitrogen oxides
ITMI20010336U1 (en) * 2001-06-20 2002-12-20 Cadif Srl MEMBRANE WITH METALLIC CORE FOR WATERPROOFING AND STRUCTURAL PROTECTIONS, ELECTROTHERMIC
US8079845B2 (en) * 2005-05-10 2011-12-20 Environmental Energy Services, Inc. Processes for operating a utility boiler and methods therefor
US20080006519A1 (en) * 2006-07-06 2008-01-10 Badger Phillip C Method and system for accomplishing flash or fast pyrolysis with carbonaceous materials
CN101558009B (en) * 2006-12-11 2012-03-28 巴斯夫欧洲公司 Method for isolating N2O
ITMI20072290A1 (en) * 2007-12-06 2009-06-07 Itea Spa COMBUSTION PROCESS
US20100139155A1 (en) * 2009-01-26 2010-06-10 Mennell James A Switch grass fuel objects with high heat output and reduced air emissions designed for large-scale power generation
US20100139156A1 (en) * 2009-01-26 2010-06-10 Mennell James A Corn stover fuel objects with high heat output and reduced emissions designed for large-scale power generation
WO2011019901A1 (en) * 2009-08-14 2011-02-17 Badger Phillip C Plant for the flash or fast pyrolysis of carbonaceous materials
CA2833286C (en) 2011-04-15 2020-08-25 Biogenic Reagents LLC Systems and apparatus for production of high-carbon biogenic reagents
EP3702325A1 (en) 2012-05-07 2020-09-02 Carbon Technology Holdings, LLC Process for producing energy
WO2015061701A1 (en) 2013-10-24 2015-04-30 Biogenic Reagent Ventures, Llc Methods and apparatus for producing activated carbon from biomass through carbonized ash intermediates
US9724667B2 (en) 2014-01-16 2017-08-08 Carbon Technology Holdings, LLC Carbon micro-plant
WO2015127460A1 (en) 2014-02-24 2015-08-27 Biogenic Reagent Ventures, Llc Highly mesoporous activated carbon
WO2016065357A1 (en) 2014-10-24 2016-04-28 Biogenic Reagent Ventures, Llc Halogenated activated carbon compositions and methods of making and using same
CN108744922A (en) * 2018-07-03 2018-11-06 山东寿光巨能金玉米开发有限公司 A kind of tube bank waste heat exhaust gas treating method and dedicated unit applied to production of corn starch field
US20220098685A1 (en) 2020-09-25 2022-03-31 Carbon Technology Holdings, LLC Bio-reduction of metal ores integrated with biomass pyrolysis
US11851723B2 (en) 2021-02-18 2023-12-26 Carbon Technology Holdings, LLC Carbon-negative metallurgical products
CN117440864A (en) 2021-04-27 2024-01-23 卡本科技控股有限责任公司 Biochar compositions with optimized fixed carbon and methods of producing the same
CN117916204A (en) 2021-07-09 2024-04-19 卡本科技控股有限责任公司 Method for producing biochar pellets with high fixed carbon content and optimized reactivity and biochar pellets obtained therefrom
CN113698603B (en) * 2021-08-21 2022-05-17 昆明理工大学 Method for preparing sulfur-containing high-molecular functional material by using sulfur dioxide flue gas

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2908322A1 (en) * 1979-03-03 1980-09-04 Heinz Ing Grad Hoelter Sulphur di:oxide gas scrubbing process - using clear or turbid liquor according to gas compsn.
US4613487A (en) * 1985-03-22 1986-09-23 Conoco Inc. Flue gas desulfurization process
US4615871A (en) * 1985-03-22 1986-10-07 Conoco Inc. Flue gas desulfurization process
WO1993001125A1 (en) * 1991-07-03 1993-01-21 Radian Corporation Cocurrent scrubber method and system

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR553704A (en) * 1922-07-05 1923-05-29 Method of methodical treatment of black water resulting from the leaching with caustic soda of various plants, with a view to the separation of the bodies they contain
US1917660A (en) * 1928-07-09 1933-07-11 Commercial Solvents Corp Method of separating and recovering acetic and butyric acids
US3970434A (en) * 1974-10-07 1976-07-20 The United States Of America As Represented By The United States Energy Research And Development Administration Process for reducing sulfur in coal char
US4259085A (en) * 1977-01-27 1981-03-31 Dravo Corporation Pelletized fixed sulfur fuel
US4319885A (en) * 1980-09-08 1982-03-16 Aluminum Company Of America Coal fuel mixture resulting in reduced sulfurous pollutants
US4505776A (en) * 1982-07-08 1985-03-19 Wescam Services Inc. Composition and method for treating flue gas and methanol containing effluents
US4728393A (en) * 1985-11-20 1988-03-01 Domtar Inc. Methods for obtaining deicers from black liquor
US4786485A (en) * 1986-11-12 1988-11-22 The United States Of America As Represented By The United States Environmental Protection Agency Lignosulfonate-modified calcium hydroxide for SO2 control during furnace injection
US5288857A (en) * 1988-12-12 1994-02-22 Ligno Tech Sweden Ab Lignin preparation and method for its manufacture
US5458803B1 (en) * 1993-09-30 1999-08-03 Dynamotive Corp Acid emission reduction

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2908322A1 (en) * 1979-03-03 1980-09-04 Heinz Ing Grad Hoelter Sulphur di:oxide gas scrubbing process - using clear or turbid liquor according to gas compsn.
US4613487A (en) * 1985-03-22 1986-09-23 Conoco Inc. Flue gas desulfurization process
US4615871A (en) * 1985-03-22 1986-10-07 Conoco Inc. Flue gas desulfurization process
WO1993001125A1 (en) * 1991-07-03 1993-01-21 Radian Corporation Cocurrent scrubber method and system

Also Published As

Publication number Publication date
BR9407727A (en) 1997-02-12
US5458803B1 (en) 1999-08-03
DK0721367T3 (en) 1999-04-26
SI9420056A (en) 1996-10-31
JPH09505768A (en) 1997-06-10
DE69411931D1 (en) 1998-08-27
TW320569B (en) 1997-11-21
CN1133569A (en) 1996-10-16
CZ92296A3 (en) 1996-09-11
EP0721367A1 (en) 1996-07-17
CA2172846A1 (en) 1995-04-06
DE69411931T2 (en) 1999-04-01
US5645805B1 (en) 2000-01-11
LV11533B (en) 1997-06-20
US5645805A (en) 1997-07-08
AU677436B2 (en) 1997-04-24
LV11533A (en) 1996-10-20
EP0721367B1 (en) 1998-07-22
NZ273900A (en) 1996-11-26
CN1068242C (en) 2001-07-11
ES2122331T3 (en) 1998-12-16
US5458803A (en) 1995-10-17
ATE168580T1 (en) 1998-08-15
KR960704617A (en) 1996-10-09
PL313764A1 (en) 1996-07-22
SK42996A3 (en) 1996-11-06
AU7737394A (en) 1995-04-18

Similar Documents

Publication Publication Date Title
US5458803A (en) Acid emission reduction
US5817282A (en) Reduction of nitrogen oxides
US4113615A (en) Method for obtaining substantially complete removal of phenols from waste water
US5499587A (en) Sulfur-sorbent promoter for use in a process for the in-situ production of a sorbent-oxide aerosol used for removing effluents from a gaseous combustion stream
KR20110095294A (en) Method and apparatus for treating an off-gas stream
US5352370A (en) Method for SOx removal by catalytic carbon
JPS63501031A (en) Method for reducing nitrogen oxide and sulfur oxide emissions during combustion of nitrogen and sulfur containing fuels
US4976937A (en) Sulfur dioxide removal from flue gases with sulfite oxidation inhibition
US4472364A (en) Process for removal of sulfur oxides from hot gases
US4980138A (en) Removal of SOx and NOx gases from flue gas by dry absorption using an absorbent
US4956161A (en) Process for removing SO from a gaseous mixture (OP-3409)
WO1996020779A1 (en) Fertilizers for agricultural soils by entrapment of acid gases
WO2010129522A1 (en) Removing a heavy metal from a combustion gas
USH1539H (en) Method of reducing hydrogen chloride in synthesis gas
US5084257A (en) Sulfur dioxide removal from stack gas
JP2002161290A (en) Coal briquette solid fuel
CA1050732A (en) Process for the treatment of gas streams containing hydrogen cyanide
DE3726665C2 (en)
US4086324A (en) Removal of sulfur and nitrogen oxides with aqueous absorbent
CS274269B2 (en) Method of sulphur dioxide removal from fue gases
DE2000059C3 (en) Process for the desulphurization of combustion gases
US5961844A (en) Process for the removal of NOx from a fluid stream
US4622213A (en) Sulfur dioxide removal from gas streams
RU96108792A (en) METHOD FOR REDUCING ACID EMISSIONS FROM SMOKE GAS, LIQUID ADDITIVE AND METHOD FOR PRODUCING LIQUID ADDITIVE
CN112138723A (en) Desulfurization catalyst and preparation method thereof

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 94193926.X

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK ES FI GB GE HU JP KE KG KP KR KZ LK LT LU LV MD MG MN MW NL NO NZ PL PT RO RU SD SE SI SK TJ TT UA UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE MW SD SZ AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2172846

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 273900

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: PV1996-922

Country of ref document: CZ

Ref document number: 42996

Country of ref document: SK

WWE Wipo information: entry into national phase

Ref document number: 1994928240

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1994928240

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: PV1996-922

Country of ref document: CZ

WWG Wipo information: grant in national office

Ref document number: 1994928240

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: PV1996-922

Country of ref document: CZ