CA2152786A1 - A method of processing tar and similar products, the use of the resulting products, and fuels obtainable by the method - Google Patents
A method of processing tar and similar products, the use of the resulting products, and fuels obtainable by the methodInfo
- Publication number
- CA2152786A1 CA2152786A1 CA 2152786 CA2152786A CA2152786A1 CA 2152786 A1 CA2152786 A1 CA 2152786A1 CA 2152786 CA2152786 CA 2152786 CA 2152786 A CA2152786 A CA 2152786A CA 2152786 A1 CA2152786 A1 CA 2152786A1
- Authority
- CA
- Canada
- Prior art keywords
- alkaline
- compounds
- dispersion
- products
- alkaline earth
- Prior art date
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
Abstract
A method is described of processing tar, tar products, distillation-, coke oven plant- and oil residues and similar organic compounds consisting of aromatics and other hydrocarbons or containing the latter, wherein the products to be processed are treated with one or more inorganic alkaline compounds. Fluid aqueous dispersions or solids are thus obtained, each of which can be employed as fuels.
Description
- 21 5Z78~
5 A method of proc~c.cin~ tar and similar products, the use of the resultino products~
and fuels obtainable bv the method.
This invention relates to a method of processing tar, tar products, distillation-, coke oven plant- and oil residues and similar, liquid or viscous organic compounds consisting of 10 aromatics and other hydrocarbons or cont~ining the latter, to the use of the resulting products, and to fuels obtainable by the method.
The term "tar" comprises liquid to semi-solid, brown to jet black decomposition products which are formed during the thermal treatment of coal, wood, peat, oil and the like. A
15 distinction is made between tars from hard coal, lignite, wood, peat and oil. In addition, viscous organic compounds which consist of aromatics and other hydrocarbons or which contain the latter are formed during distillation processes and other industrial processes.
These compounds have properties similar to those of tar. The products which are to be processed according to the invention are also to be understood to include residues from ~O accidents involving oil-transporting vehicles, which have a serious pollutant effect on the environment.
If they are improperly handled, even the said products themselves constitute an environmental hazard. Furthermore, they may contain other environmentally harmful ~S substances such as phenols, oils containing naphthenic acid, and heterocyclic compounds.
A common feature of the said materials is that they range from the highly viscous to the fluid and sticky and they also have unpleasant odours. Due to their high viscosities they cannot be pumped and are otherwise difficult to handle. They are difficult to load or 30 Iransport using dredgers or excavators or similar devices, for example.
2l52786 In the past, the said products have sometimes been improperly dumped. Waste dumps of this type constitute a considerable environmental hazard, and their disposal is a serious problem.
5 Attempts have sometimes been made in the past to dissolve the said products in organic solvents to convert them into a handleable form. This is financially costly, however, and is associated with further environmental hazards.
The object of the present invention is to provide a method of the type cited at the outset 10 which ensures that these products are disposed of or processed in an economical and environmentally friendly manner. The aim of the method according to the invention is to create products which can be handled, i.e. pumped or transported, and which can be supplied for further utilisation if possible or can at least be dumped without problems.
15 It has surprisingly been found that the use of organic solvents can be dispensed with and that the said tar products can be converted into easily handleable dispersions of low viscosity or into solid materials which can be dumped, by using aqueous solutions or slurries of inorganic alkaline compounds, wherein both the dispersions and the solids can be employed as liquid and solid fuels, respectively.
~0 The present invention therefore relates to a method of processing tar, tar products~
distillation-, coke oven plant- and oil residues and similar organic compounds consisting of aromatics and other hydrocarbons or containing the latter, which is characterised in that the products to be processed are treated with one or more inorganic alkaline ~5 compounds.
For example, the products to be processed can be treated with aqueous solutions or slurries of one or more inorganic alkaline compounds. In this manner it is possible in particular to process viscous products and to convert them into liquid dispersions.
- 21~2786 However, it is also possible to treat the products to be processed with alkalinecompounds of alkaline earth metals and alkaline aluminium compounds. In this manner, liquid products in particular can be treated and converted into a solid form.
A particularly preferred embodiment of the invention relates to a method of processing tar, tar products, distiliation-, coke oven plant- and oil residues and similar, viscous organic compounds consisting of aromatics and other hydrocarbons or cont~ining the latter, which is characterised in that the products to be processed are converted into a dispersion with the addition of aqueous solutions or slurries of one or more inorganic alkaline compounds, and the dispersion obtained is optionally converted into a solid form, even during the dispersion step or in a further process step, in the presence of alkaline compounds of alkaline earth metals and alkaline aluminium compounds.
Within the scope of the invention it has been shown that the desired dispersion can be effected using aqueous solutions or slurries of alkaline compounds. Alkali metalhydroxides, alkali metal oxides, ammonia, alkali metal aluminates, ammonium aluminate or mixtures thereof can be used for this purpose, for example. Water-soluble ~Ik~line compounds are preferred; however, it is also possible to use alkaline compounds which can form a slurry in water. It has been shown that the method can also be carried out ~0 using alkaline earth metal hydroxides and oxides, optionally in admixture with alkali metal hydroxides and oxides.
Examples of suitable alkali metal hydroxides include sodium hydroxide or potassium hydroxide, calcium hydroxide and magnesium hydroxide are particularly suitable as ~5 alkaline earth metal hydroxides, and calcium oxide is particularly suitable as an alkaline earth metal oxide.
The alkaline solutions or slurries for the method of processing according to the invention preferably contain alkaline compounds in amounts of 1 to 60 weight %, most preferably 1 to 40 weighl %, at a water content of 99 to 40 weight %, preferably 99 to 60 weight %.
- 215278~
Alkali aluminates such as sodium or potassium ahlmin~t~, alkaline earth ahlmin~tes such as calcium aluminate, ammonium aluminate, or compounds cont~ining ahlmin~te suchas alumina or cements, or mixtures of two or more of the said substances, are advantageously used as the water-soluble aluminates. The ahlmin~tes may also be 5 formed in situ, for example from freshly precipitated aluminium hydroxide by the addition of alkali hydroxides such as sodium hydroxide, or of alkaline earth metal hydroxides such as calcium hydroxide. For example, aluminium hydroxide can be precipitated from a solution of an aluminium salt, such as aluminium chloride, with an alkali, such as sodium hydroxide or calcium hydroxide, and dissolved to form the10 corresponding ahlmin~te.
The solidification of liquid products or dispersions may also be effected solely by the addition of alkaline earth metal aluminates, instead of the mixture of an ahlmin~te and an alkaline compound of an alkaline earth metal. In this respect, the alkaline earth metal 15 ahlmin~te may be used in aqueous form or also in anhydrous (dehydrated) form.
In order to speed up the dispersion of the products to be processed, mechanical energy can be used according to the invention. This can advantageously be effected by stirring, sparging, shaking or mixing. Stirring is generally preferred for practical reasons. In ~0 this connection, the usual stirrer or mixer units can be used, such as paddle mixers or positive mixers, and also dissolvers and similar apparatuses known in the prior art. It is essential that adequate shearing forces result in rapid dispersion.
In order to speed up or facilitate dispersion, it is also possible to heat the solutions or 25 dispersions used. The temperature to which they are heated may for example be up to 90C, preferably up to 50C.
Advantageously, 90 to 5 parts by weight of the said solutions or slurries of calcium compounds and/or ahlmin~tes are used for 10 to 95 parts by weight of the product to be 30 processed; preferably, 50 to 25 parts by weight of the solutions or slurries are used for 50 to 75 parts by weight of the product to be processed, wherein the sum of the parts by weight gives 100 parts by weight of dispersion. If a smaller amount of the solution ~1527~6 or slurry acting as the dispersing agent is used with respect lo the amount of product to be processed, the dispersion step is generally not satisfactory. In fact larger amounts result in a satisfactory dispersion step, but they unnecessarily dilute the dispersion ob~ained and are therefore undesirable for economic reasons.
s The surface of the products to be processed is advantageously covered before effecting dispersion with a pasty slurry containing calcium compounds and aluminates, into which carbon dioxide or air is introduced.
10 The underlying object of the invention is advantageously achieved by means of the method described. The products to be processed are converted into an easily handled dispersion, i.e. into a dispersion which can be pumped and transported, which can be used as a fuel or can be fed to a further processing stage.
15 According to a further aspect of the invention, the dispersions obtained can be converted into a solid form, even during the dispersion step but also in a second process step, by the addition of alkali or alkaline earth aluminate and/or mixtures of calcium compounds and ahlmin~tes, aluminium hydroxide and or aluminium oxide. The use of aluminiumhydroxide and/or aluminium oxide is particularly advantageous, since further waste ~0 materials can be used here. For example, aluminium oxide is formed in the so-called anodising process; waste products of this type previously had ~o be deposited in waste dumps. The compounds described above can be used as the alkali or alkaline earthaluminates .
~5 If the dispersion already contains alkaline earth compounds. it may be sufficient to treat it with one or more alkaline aluminium compounds.
If. on the other hand, the dispersion already contains aluminate, it may be sufficient for solidification to add one or more alkaline compounds of alkaline earth metals.
For solidification, the alkaline earth metal compounds as well as the aluminium compounds may be used in dissolved or slurried aqueous form or in solid form without water. Thus it is possible to use aluminates in hydrated and also in dehydrated form, for example.
On the addition of alllmin~res to calcium compounds definite compounds are formed in S the presence of water. These compounds may be obtained in situ during the solidification, or they may be prepared previously and then added. They have a lamellar structure comprising layers of cations and anions of the following formulae:
Cationic primary layer:
Ca4[AI7(0H)I7]2+
Anionic intermediate layer:
S [X7 aq]'~ or [Y . aq]~~, where X is a monovalent anion such as OH-, Cl~ or NO3-, and Y is a divalent anion such as S04'- or CO;'~, ~0 and where aq represents water.
The amount of water of crystallisation depends on the preparation conditions, particularly on the temperature and pH; in practice it is of the order of 6 to 12 molecules of water per anion.
'S
Compounds containing carbonate can also be used for the solidification according to the invention. In particular, it has been shown that carbonate-containing modifications of the absorption media described are particularly stable. These can be formed from the above-mentioned compounds, for example, where X or Y are different from carbonate, 30 by the addition of carbonate ions or by working in the presence of carbon dioxide or of a gas containing carbon dioxide. The X or Y anions are then replaced by carbonate anions. The carbonates may also be produced directly if the absorption media are produced from the outset in the presence of carbonate ions and/or carbon dioxide. The carbonates are present as monocarbonate or semicarbonate, in which the cationic primary layer is unchanged but the anionic intermediate layer has the following formulae:
5 semicarbonate:
[OH/O, SC03 . aq]2~
monocarbonate:
[C03 . aq]2~
Surprisingly, it has been shown within the scope of the invention that organic molecules can be intercalated in the structures of the above-mentioned compounds. It can therefore 15 be assumed that organic compounds are incorporated in the intermediate layers of the lamellar structures, replacing at least part of the water of hydralion there. Ions and polar organic pollutants can also completely or partially replace the X or Y anion of the intermediate layer.
~0 Tests with anthracene showed, for example, that absorption of anthracene occurred on the monocarbonate, resulting in the following definite crystalline chemical compound:
[Ca4Al~-(OH)I2]2+ [C03 AC/H~0]2-~5 where AC = anthracene.
Tests with anthracene carboxylic acid (ACC) resulted in the formation of the following compound:
30 ICa4Al~(OH)I2]~+ [ACC nH20]~
(n depends on the temperature and atmospheric humidity).
The solutions or slurries containing calcium compounds and aluminates which can be used according to the invention can be prepared in various ways. In principle, it is sufficient to mix the calcium compound with the aluminate. Water may be added previously or afterwards. If the corresponding monocarbonate or semicarbonate S compound is prepared, carbonate and/or carbon dioxide must be present before, during or after the reaction of the calcium compound with the alllmin~te.
For example, it is possible to mix the calcium compound, such as dry lime (CaO), with dry alllmin~, such as sodium all1min~te, then to mix with water and optionally to add 10 carbonate ions and/or carbon dioxide.
A solution or slurry is advantageously used which has a content of 1 to 60 weight %, preferably 10 to 40 weight %, of calcium compounds and/or 1 to 40 weight % of aluminates, calculated as Al,03. Aqueous solutions or slurries which contain a total of 15 20 to 30 weight % of the said substances are particularly preferred.
Depending on the amount of alkali or alkaline earth aluminates used, crumb-like products, ranging from moist to dry, are produced in the solidification step which can optionally be carried out according to the invention. In contrast to the starting materials, ~0 these products are no longer semi-liquid, viscous and sticky, but can be conveyed and transported in a simple manner. The solidified products can be used as solid fuel or dumped in accordance with the regulations. In order to achieve solidification, which may also be considered as a thickening or drying process, the alkali and/or alkaline earth alllmin~t~s are preferably stirred into the dispersion produced by the method ~5 described at the outset in solid form or as a solution or slurry as in the first process step.
In this respect the amount is calculated so that the desired solidification is achieved. In general, it is sufficient to use 1 to 50 weight %, preferably 10 to 30 weight %, of alkali or alkaline earth aluminates with respect to the dispersion.
30 Aggregate materials which additionally assist solidification, such as fly ash, gypsum or limestone, can advantageously be added to the dispersion. If fly ash is used, fly ash from lignite is preferred, because this results in a particularly favourable solidification - 21 5278~
due to its pozzolanic properties. The said aggregate materials not only improve solidification, but also reduce the gross calorific value of the final product obtained.
This is advantageous inasmuch as the gross calorific value of the starting materials is too high for many conventional combustion installations.
The present invention also relates to the use of the dispersions produced in the first process step as a liquid fuel, to the use of the solids produced in the second process step as a solid fuel, and to the liquid and solid fuels per se. The dispersions or solid fuels are preferably not used as the only fuel, but are used as additional fuels in existing 10 combustion installations which generate heat energy by the combustion of coal, coke, oil or gas and of combustible refuse.
If the starting materials to be processed are contaminated with heavy metals, a further advantage arises in that completely insoluble heavy metal oxides are formed when the 15 final products produced according to the invention are heated. In particular. compounds of the so-called spinel type are formed, which are particularly stable. In addition, the basic properties obtained when calcium oxide or calcium hydroxide and alkali ah]min~te and/or alkaline earth aluminate are used result in advantageous behaviour on combustion, in a manner such that acidic gases formed on combustion, such as S07 or volatile~0 chlorides for example, are partially bound and their emission is reduced. These effects comprise further aspects of the present invention which are advantageous from anenvironmental point of view.
On combustion, the basic components result in an advantageous reduction of emissions, 25 due to the bonding of acidic components.
The ash formed on the combustion of the liquid fuel or of the solid fuel acquires an enhanced pozzolanic character due to its calcium and aluminium content. This favours the suitability of the ash for being dumped.
The invention is described in more detail below by way of an example. The percentages given are in weight %.
lo Example 1 100 g of a 20 % sodium aluminate solution (20 weight % Al~03) are added to 1000 g of tar residue and slowly stirred in. A dispersion with good handling properties is 5 obtained, which can be used as a liquid fuel.
Solidification is effected by the addition of 7500 g of 20 % milk of lime. The product obtained is crumb-like, moist and easily handled, and can be used as a solid fuel.
5 A method of proc~c.cin~ tar and similar products, the use of the resultino products~
and fuels obtainable bv the method.
This invention relates to a method of processing tar, tar products, distillation-, coke oven plant- and oil residues and similar, liquid or viscous organic compounds consisting of 10 aromatics and other hydrocarbons or cont~ining the latter, to the use of the resulting products, and to fuels obtainable by the method.
The term "tar" comprises liquid to semi-solid, brown to jet black decomposition products which are formed during the thermal treatment of coal, wood, peat, oil and the like. A
15 distinction is made between tars from hard coal, lignite, wood, peat and oil. In addition, viscous organic compounds which consist of aromatics and other hydrocarbons or which contain the latter are formed during distillation processes and other industrial processes.
These compounds have properties similar to those of tar. The products which are to be processed according to the invention are also to be understood to include residues from ~O accidents involving oil-transporting vehicles, which have a serious pollutant effect on the environment.
If they are improperly handled, even the said products themselves constitute an environmental hazard. Furthermore, they may contain other environmentally harmful ~S substances such as phenols, oils containing naphthenic acid, and heterocyclic compounds.
A common feature of the said materials is that they range from the highly viscous to the fluid and sticky and they also have unpleasant odours. Due to their high viscosities they cannot be pumped and are otherwise difficult to handle. They are difficult to load or 30 Iransport using dredgers or excavators or similar devices, for example.
2l52786 In the past, the said products have sometimes been improperly dumped. Waste dumps of this type constitute a considerable environmental hazard, and their disposal is a serious problem.
5 Attempts have sometimes been made in the past to dissolve the said products in organic solvents to convert them into a handleable form. This is financially costly, however, and is associated with further environmental hazards.
The object of the present invention is to provide a method of the type cited at the outset 10 which ensures that these products are disposed of or processed in an economical and environmentally friendly manner. The aim of the method according to the invention is to create products which can be handled, i.e. pumped or transported, and which can be supplied for further utilisation if possible or can at least be dumped without problems.
15 It has surprisingly been found that the use of organic solvents can be dispensed with and that the said tar products can be converted into easily handleable dispersions of low viscosity or into solid materials which can be dumped, by using aqueous solutions or slurries of inorganic alkaline compounds, wherein both the dispersions and the solids can be employed as liquid and solid fuels, respectively.
~0 The present invention therefore relates to a method of processing tar, tar products~
distillation-, coke oven plant- and oil residues and similar organic compounds consisting of aromatics and other hydrocarbons or containing the latter, which is characterised in that the products to be processed are treated with one or more inorganic alkaline ~5 compounds.
For example, the products to be processed can be treated with aqueous solutions or slurries of one or more inorganic alkaline compounds. In this manner it is possible in particular to process viscous products and to convert them into liquid dispersions.
- 21~2786 However, it is also possible to treat the products to be processed with alkalinecompounds of alkaline earth metals and alkaline aluminium compounds. In this manner, liquid products in particular can be treated and converted into a solid form.
A particularly preferred embodiment of the invention relates to a method of processing tar, tar products, distiliation-, coke oven plant- and oil residues and similar, viscous organic compounds consisting of aromatics and other hydrocarbons or cont~ining the latter, which is characterised in that the products to be processed are converted into a dispersion with the addition of aqueous solutions or slurries of one or more inorganic alkaline compounds, and the dispersion obtained is optionally converted into a solid form, even during the dispersion step or in a further process step, in the presence of alkaline compounds of alkaline earth metals and alkaline aluminium compounds.
Within the scope of the invention it has been shown that the desired dispersion can be effected using aqueous solutions or slurries of alkaline compounds. Alkali metalhydroxides, alkali metal oxides, ammonia, alkali metal aluminates, ammonium aluminate or mixtures thereof can be used for this purpose, for example. Water-soluble ~Ik~line compounds are preferred; however, it is also possible to use alkaline compounds which can form a slurry in water. It has been shown that the method can also be carried out ~0 using alkaline earth metal hydroxides and oxides, optionally in admixture with alkali metal hydroxides and oxides.
Examples of suitable alkali metal hydroxides include sodium hydroxide or potassium hydroxide, calcium hydroxide and magnesium hydroxide are particularly suitable as ~5 alkaline earth metal hydroxides, and calcium oxide is particularly suitable as an alkaline earth metal oxide.
The alkaline solutions or slurries for the method of processing according to the invention preferably contain alkaline compounds in amounts of 1 to 60 weight %, most preferably 1 to 40 weighl %, at a water content of 99 to 40 weight %, preferably 99 to 60 weight %.
- 215278~
Alkali aluminates such as sodium or potassium ahlmin~t~, alkaline earth ahlmin~tes such as calcium aluminate, ammonium aluminate, or compounds cont~ining ahlmin~te suchas alumina or cements, or mixtures of two or more of the said substances, are advantageously used as the water-soluble aluminates. The ahlmin~tes may also be 5 formed in situ, for example from freshly precipitated aluminium hydroxide by the addition of alkali hydroxides such as sodium hydroxide, or of alkaline earth metal hydroxides such as calcium hydroxide. For example, aluminium hydroxide can be precipitated from a solution of an aluminium salt, such as aluminium chloride, with an alkali, such as sodium hydroxide or calcium hydroxide, and dissolved to form the10 corresponding ahlmin~te.
The solidification of liquid products or dispersions may also be effected solely by the addition of alkaline earth metal aluminates, instead of the mixture of an ahlmin~te and an alkaline compound of an alkaline earth metal. In this respect, the alkaline earth metal 15 ahlmin~te may be used in aqueous form or also in anhydrous (dehydrated) form.
In order to speed up the dispersion of the products to be processed, mechanical energy can be used according to the invention. This can advantageously be effected by stirring, sparging, shaking or mixing. Stirring is generally preferred for practical reasons. In ~0 this connection, the usual stirrer or mixer units can be used, such as paddle mixers or positive mixers, and also dissolvers and similar apparatuses known in the prior art. It is essential that adequate shearing forces result in rapid dispersion.
In order to speed up or facilitate dispersion, it is also possible to heat the solutions or 25 dispersions used. The temperature to which they are heated may for example be up to 90C, preferably up to 50C.
Advantageously, 90 to 5 parts by weight of the said solutions or slurries of calcium compounds and/or ahlmin~tes are used for 10 to 95 parts by weight of the product to be 30 processed; preferably, 50 to 25 parts by weight of the solutions or slurries are used for 50 to 75 parts by weight of the product to be processed, wherein the sum of the parts by weight gives 100 parts by weight of dispersion. If a smaller amount of the solution ~1527~6 or slurry acting as the dispersing agent is used with respect lo the amount of product to be processed, the dispersion step is generally not satisfactory. In fact larger amounts result in a satisfactory dispersion step, but they unnecessarily dilute the dispersion ob~ained and are therefore undesirable for economic reasons.
s The surface of the products to be processed is advantageously covered before effecting dispersion with a pasty slurry containing calcium compounds and aluminates, into which carbon dioxide or air is introduced.
10 The underlying object of the invention is advantageously achieved by means of the method described. The products to be processed are converted into an easily handled dispersion, i.e. into a dispersion which can be pumped and transported, which can be used as a fuel or can be fed to a further processing stage.
15 According to a further aspect of the invention, the dispersions obtained can be converted into a solid form, even during the dispersion step but also in a second process step, by the addition of alkali or alkaline earth aluminate and/or mixtures of calcium compounds and ahlmin~tes, aluminium hydroxide and or aluminium oxide. The use of aluminiumhydroxide and/or aluminium oxide is particularly advantageous, since further waste ~0 materials can be used here. For example, aluminium oxide is formed in the so-called anodising process; waste products of this type previously had ~o be deposited in waste dumps. The compounds described above can be used as the alkali or alkaline earthaluminates .
~5 If the dispersion already contains alkaline earth compounds. it may be sufficient to treat it with one or more alkaline aluminium compounds.
If. on the other hand, the dispersion already contains aluminate, it may be sufficient for solidification to add one or more alkaline compounds of alkaline earth metals.
For solidification, the alkaline earth metal compounds as well as the aluminium compounds may be used in dissolved or slurried aqueous form or in solid form without water. Thus it is possible to use aluminates in hydrated and also in dehydrated form, for example.
On the addition of alllmin~res to calcium compounds definite compounds are formed in S the presence of water. These compounds may be obtained in situ during the solidification, or they may be prepared previously and then added. They have a lamellar structure comprising layers of cations and anions of the following formulae:
Cationic primary layer:
Ca4[AI7(0H)I7]2+
Anionic intermediate layer:
S [X7 aq]'~ or [Y . aq]~~, where X is a monovalent anion such as OH-, Cl~ or NO3-, and Y is a divalent anion such as S04'- or CO;'~, ~0 and where aq represents water.
The amount of water of crystallisation depends on the preparation conditions, particularly on the temperature and pH; in practice it is of the order of 6 to 12 molecules of water per anion.
'S
Compounds containing carbonate can also be used for the solidification according to the invention. In particular, it has been shown that carbonate-containing modifications of the absorption media described are particularly stable. These can be formed from the above-mentioned compounds, for example, where X or Y are different from carbonate, 30 by the addition of carbonate ions or by working in the presence of carbon dioxide or of a gas containing carbon dioxide. The X or Y anions are then replaced by carbonate anions. The carbonates may also be produced directly if the absorption media are produced from the outset in the presence of carbonate ions and/or carbon dioxide. The carbonates are present as monocarbonate or semicarbonate, in which the cationic primary layer is unchanged but the anionic intermediate layer has the following formulae:
5 semicarbonate:
[OH/O, SC03 . aq]2~
monocarbonate:
[C03 . aq]2~
Surprisingly, it has been shown within the scope of the invention that organic molecules can be intercalated in the structures of the above-mentioned compounds. It can therefore 15 be assumed that organic compounds are incorporated in the intermediate layers of the lamellar structures, replacing at least part of the water of hydralion there. Ions and polar organic pollutants can also completely or partially replace the X or Y anion of the intermediate layer.
~0 Tests with anthracene showed, for example, that absorption of anthracene occurred on the monocarbonate, resulting in the following definite crystalline chemical compound:
[Ca4Al~-(OH)I2]2+ [C03 AC/H~0]2-~5 where AC = anthracene.
Tests with anthracene carboxylic acid (ACC) resulted in the formation of the following compound:
30 ICa4Al~(OH)I2]~+ [ACC nH20]~
(n depends on the temperature and atmospheric humidity).
The solutions or slurries containing calcium compounds and aluminates which can be used according to the invention can be prepared in various ways. In principle, it is sufficient to mix the calcium compound with the aluminate. Water may be added previously or afterwards. If the corresponding monocarbonate or semicarbonate S compound is prepared, carbonate and/or carbon dioxide must be present before, during or after the reaction of the calcium compound with the alllmin~te.
For example, it is possible to mix the calcium compound, such as dry lime (CaO), with dry alllmin~, such as sodium all1min~te, then to mix with water and optionally to add 10 carbonate ions and/or carbon dioxide.
A solution or slurry is advantageously used which has a content of 1 to 60 weight %, preferably 10 to 40 weight %, of calcium compounds and/or 1 to 40 weight % of aluminates, calculated as Al,03. Aqueous solutions or slurries which contain a total of 15 20 to 30 weight % of the said substances are particularly preferred.
Depending on the amount of alkali or alkaline earth aluminates used, crumb-like products, ranging from moist to dry, are produced in the solidification step which can optionally be carried out according to the invention. In contrast to the starting materials, ~0 these products are no longer semi-liquid, viscous and sticky, but can be conveyed and transported in a simple manner. The solidified products can be used as solid fuel or dumped in accordance with the regulations. In order to achieve solidification, which may also be considered as a thickening or drying process, the alkali and/or alkaline earth alllmin~t~s are preferably stirred into the dispersion produced by the method ~5 described at the outset in solid form or as a solution or slurry as in the first process step.
In this respect the amount is calculated so that the desired solidification is achieved. In general, it is sufficient to use 1 to 50 weight %, preferably 10 to 30 weight %, of alkali or alkaline earth aluminates with respect to the dispersion.
30 Aggregate materials which additionally assist solidification, such as fly ash, gypsum or limestone, can advantageously be added to the dispersion. If fly ash is used, fly ash from lignite is preferred, because this results in a particularly favourable solidification - 21 5278~
due to its pozzolanic properties. The said aggregate materials not only improve solidification, but also reduce the gross calorific value of the final product obtained.
This is advantageous inasmuch as the gross calorific value of the starting materials is too high for many conventional combustion installations.
The present invention also relates to the use of the dispersions produced in the first process step as a liquid fuel, to the use of the solids produced in the second process step as a solid fuel, and to the liquid and solid fuels per se. The dispersions or solid fuels are preferably not used as the only fuel, but are used as additional fuels in existing 10 combustion installations which generate heat energy by the combustion of coal, coke, oil or gas and of combustible refuse.
If the starting materials to be processed are contaminated with heavy metals, a further advantage arises in that completely insoluble heavy metal oxides are formed when the 15 final products produced according to the invention are heated. In particular. compounds of the so-called spinel type are formed, which are particularly stable. In addition, the basic properties obtained when calcium oxide or calcium hydroxide and alkali ah]min~te and/or alkaline earth aluminate are used result in advantageous behaviour on combustion, in a manner such that acidic gases formed on combustion, such as S07 or volatile~0 chlorides for example, are partially bound and their emission is reduced. These effects comprise further aspects of the present invention which are advantageous from anenvironmental point of view.
On combustion, the basic components result in an advantageous reduction of emissions, 25 due to the bonding of acidic components.
The ash formed on the combustion of the liquid fuel or of the solid fuel acquires an enhanced pozzolanic character due to its calcium and aluminium content. This favours the suitability of the ash for being dumped.
The invention is described in more detail below by way of an example. The percentages given are in weight %.
lo Example 1 100 g of a 20 % sodium aluminate solution (20 weight % Al~03) are added to 1000 g of tar residue and slowly stirred in. A dispersion with good handling properties is 5 obtained, which can be used as a liquid fuel.
Solidification is effected by the addition of 7500 g of 20 % milk of lime. The product obtained is crumb-like, moist and easily handled, and can be used as a solid fuel.
Claims (21)
1. A method of processing tar, tar products, distillation-, coke oven plant- and oil residues and similar organic compounds consisting of aromatics and other hydrocarbons or containing the latter, characterised in that the products to be processed are treated with one or more inorganic alkaline compounds.
2. A method according to claim 1, characterised in that the products to be processed are treated with aqueous solutions or slurries of one or more inorganic alkalinecompounds.
3. A method according to claim 2, characterised in that tar, tar products, distillation-, coke oven plant- and oil residues and similar organic compounds in viscous form consisting of aromatics and other hydrocarbons or containing the latter are converted into a dispersion by the addition of aqueous solutions or slurries of one or more inorganic alkaline compounds.
4. A method according to claim 1, characterised in that the products to be processed are treated with alkaline compounds of alkaline earth metals and alkaline aluminium compounds.
5. A method according to claim 4, characterised in that tar, tar products, distillation-, coke oven plant- and oil residues and similar organic compounds in liquid form consisting of aromatics and other hydrocarbons or containing the latter are converted into a solid form by the addition of alkaline compounds of alkaline earth metals and alkaline aluminium compounds.
6. A method according to any one of the preceding claims for the processing of tar, tar products, distillation-, coke oven plant- and oil residues and similar, viscous organic compounds consisting of aromatics and other hydrocarbons or containing, the latter, characterised in that the products to be processed are converted into a dispersion with the addition of aqueous solutions or slurries of one or more inorganic alkaline compounds, and the dispersion obtained is optionally converted into a solid form during dispersion or in a further process step in the presenceof alkaline compounds of alkaline earth metals and alkaline aluminium compounds.
7. A method according to claim 3 or 6, characterised in that a solution or slurry of one or more alkali metal hydroxides, alkali metal oxides, alkali metal aluminates and ammonium aluminate, optionally in admixture with each other, is used to produce the dispersion.
8. A method according to claim 3 or 4, characterised in that a solution or slurry of one or more alkaline earth metal hydroxides and alkaline earth metal oxides, optionally in admixture with one or more alkali metal hydroxides and alkali metal oxides, is used to produce the dispersion.
9. A method according to claim 7 or 8, characterised in that sodium hydroxide orpotassium hydroxide is used as the alkali metal hydroxide, calcium hydroxide or magnesium hydroxide is used as the alkaline earth metal hydroxide, calcium oxide is used as the alkaline earth metal oxide, and sodium or potassium aluminate is used as the alkali metal aluminate.
10. A method according to any one of claims 1 to 9, characterised in that the alkaline solution or slurry for preparing the dispersion has a content of alkaline compound of 1 to 60 weight % and a water content of 40 to 99 weight %.
11. A method according to any one of claims 1 to 10, characterised in that the dispersion is produced by mechanical energy, such as stirring, sparging, shaking, or mixing and/or that dispersion is effected by heating to up to 90°C.
12. A method according to any one of the preceding claims, characterised in that 90 to 5 parts by weight of a solution or slurry of alkaline compounds is used for 10 to 95 parts by weight of product to be processed.
13. A method according to any one of the preceding claims, characterised in that, for conversion into the solid form, alkaline compounds of alkaline earth metals and alkaline aluminium compounds are added to the dispersion or liquid.
14. A method according to any one of the preceding claims, characterised in that, for conversion into the solid form, one or more alkaline compounds of alkaline earthmetals are added to a dispersion which already contains aluminate and one or more alkaline aluminium compounds are added to a dispersion which already contains alkaline earth metal compounds.
15. A method according to any one of the preceding claims, characterised in that, for solidification, hydroxides, oxides and/or aluminates of calcium and/or magnesiumare used as the alkaline compounds of alkaline earth metals and alkali metal aluminates, alkaline earth metal aluminates and/or aluminium hydroxide are used as the alkaline aluminium compounds.
16. A method according to any one of the preceding claims, characterised in that, for solidification, an alkaline earth metal aluminate, particularly calcium aluminate, is used in hydrated or anhydrous form.
17. A method according to any one of the preceding claims, characterised in thataggregate materials which provide additional assistance on solidification, such as fly ash, gypsum or limestone, are added to the dispersion.
18. The use of the dispersion produced by the method of any one of the preceding claims as a liquid fuel.
19. The use of the solids produced by the method of any one of the preceding claims as a solid fuel.
20. A liquid fuel obtainable by the method according to any one of the preceding claims.
21. A solid fuel obtainable by the method according to any one of the preceding claims.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924244382 DE4244382C2 (en) | 1992-12-29 | 1992-12-29 | Process for the preparation of tar and similar products, use of the resulting products and fuels obtainable by the process |
| DEP4244382.2 | 1992-12-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2152786A1 true CA2152786A1 (en) | 1994-07-07 |
Family
ID=6476733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2152786 Abandoned CA2152786A1 (en) | 1992-12-29 | 1993-12-25 | A method of processing tar and similar products, the use of the resulting products, and fuels obtainable by the method |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0677091A1 (en) |
| JP (1) | JPH08504231A (en) |
| CA (1) | CA2152786A1 (en) |
| CZ (1) | CZ166095A3 (en) |
| DE (1) | DE4244382C2 (en) |
| PL (1) | PL309633A1 (en) |
| SK (1) | SK84495A3 (en) |
| WO (1) | WO1994014922A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858212A (en) * | 1996-07-03 | 1999-01-12 | Interglobal Desulfuruzations Systems, Inc. | Desulfurization and hydrocarbon quality enhancement process |
| WO2009072678A2 (en) * | 2008-12-08 | 2009-06-11 | Pyongyang Trading Corporation | A fuel mixture formed out of fly ash of coal and cement dust |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1212507B (en) * | 1981-10-06 | 1989-11-22 | Sistema Ecodeco S R L Ora Ecod | PROCEDURE FOR THE COLLECTION OF ACID MELME OBTAINED FROM PETROLEUM FRACTIONS, UNDER SAFETY CONDITIONS AND FOR THEIR TRANSFORMATION, IN PARTICULAR IN SOLID FUELS. |
| AT391639B (en) * | 1988-12-23 | 1990-11-12 | Perlmooser Zementwerke Ag | Method for the treatment of waste material |
| DE4015889A1 (en) * | 1990-05-17 | 1991-11-21 | Ruetgerswerke Ag | Reconditioning de:phenolated carbolic oil - by adjusting pH before distn. by slowly adding aq. lye soln. |
-
1992
- 1992-12-29 DE DE19924244382 patent/DE4244382C2/en not_active Expired - Fee Related
-
1993
- 1993-12-25 PL PL30963393A patent/PL309633A1/en unknown
- 1993-12-25 JP JP6514834A patent/JPH08504231A/en active Pending
- 1993-12-25 WO PCT/EP1993/003691 patent/WO1994014922A1/en not_active Application Discontinuation
- 1993-12-25 EP EP94903877A patent/EP0677091A1/en not_active Withdrawn
- 1993-12-25 CA CA 2152786 patent/CA2152786A1/en not_active Abandoned
- 1993-12-25 CZ CZ951660A patent/CZ166095A3/en unknown
- 1993-12-25 SK SK844-95A patent/SK84495A3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE4244382A1 (en) | 1994-06-30 |
| EP0677091A1 (en) | 1995-10-18 |
| WO1994014922A1 (en) | 1994-07-07 |
| SK84495A3 (en) | 1995-10-11 |
| CZ166095A3 (en) | 1996-03-13 |
| DE4244382C2 (en) | 1997-02-20 |
| JPH08504231A (en) | 1996-05-07 |
| PL309633A1 (en) | 1995-10-30 |
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| Date | Code | Title | Description |
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