• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a process for the treatment of wet combustion fumes, for the purification of sulfur dioxide, hydrochloric acid and the heavy metals they contain, in which: the fumes to be treated (1) are sent to an acid scrubber (101), which is supplied with lime or limestone, and then to an alkaline scrubber (102), which is fed with sodium hydroxide, the purge (4) of the acid scrubber (101) is sent to a precipitation-crystallization unit (301) after having been purified by a first water treatment, the purge (7) of the alkaline scrubber (102) is sent, separately from the acid scrubber purge, to the unit precipitation-crystallization (301) in the precipitating-crystallizing unit (301), the precipitated gypsum is formed by the Ca ++ + SO 4 - → Ca SO 4 ↓ reaction, with Ca ++ which is provided by the purge (4) of the acid scrubber (101) and SO 4 - which is provided by the purge (7) of the alkaline scrubber (102), the outlet (9) of the precipitation-crystallization unit (301), containing precipitated gypsum, is admitted into a liquid-solid separator (302) to produce a gypsum stream (10) containing less than 15% by weight of free water and intended to be recovered, and a flow of residual liquids (12), 30 to 100% in flow, preferably 50 to 80% in flow, of the flow of residual liquids (12) are purified by a second water treatment to produce a brine (15) for recovery, the remainder (14) of the residual liquid stream being recycled to one and / or the other acid (101) and alkaline washers ( 102), and the residues (5, 16) resulting from the first and second water treatments are rich in metals and are evacuated, being capable of being upgraded. The invention also relates to a wet combustion combustion treatment plant for purifying sulfur dioxide, hydrochloric acid and the heavy metals they contain.
    公开号:CH706405B1
    申请号:CH00782/13
    申请日:2013-04-16
    公开日:2018-06-29
    发明作者:Tabaries Frank；Siret Bernard
    申请人:Lab Sa；
    IPC主号:
    专利说明:

    Description: The present invention relates to a method and an installation for treating combustion smoke by the wet process.
    In this type of process, a washing liquid is brought into contact with the fumes to be purified in a washer so that the dust suspended in these fumes is transferred into the washing liquid at the same time as the gaseous pollutants, and in particular hydrochloric acid and sulfur dioxide. The flow rate of liquid necessary to ensure good purification is generally high, for example of the order of several tens to a few hundred m 3 / h, so that the liquid purge of the washer is recycled, only a small fraction of that -this being withdrawn for devolution.
    For example, in the case of a household waste incineration plant, sulfur dioxide, hydrochloric acid and heavy metals are captured in the washing purge and these pollutants must find an outlet . It can then be useful to separate the heavy metals using a water treatment. However, this water treatment will generate a sludge cake which, in addition to the precipitated metal hydroxides, often also contains gypsum.
    Furthermore, with wet scrubbers, we often have to work with two washing stages, that is to say with two successive scrubbers to treat the combustion fumes, namely an acid scrubber, operating at low pH, typically less than 4, in particular for capturing hydrochloric acid, and an alkaline washer, operating at a higher pH, typically greater than 5, for capturing in particular sulfur dioxide. To avoid having excessively large respective purges at the outlet of these two washers, a hydraulic cascade is often carried out in which the purge of one of the washers, generally the alkaline washer, is replenished in the other washer. occurrence the acid scrubber. In addition, different neutralization reagents can then be used in each of the two scrubbers, in particular limestone or lime in the acid scrubber and soda in the alkaline scrubber. In all cases, we find ourselves, ultimately, mixing the respective liquid purges of the acid and alkaline washers, while these purges have very different respective compositions, which can contribute to uncontrolled precipitation which are sources of fouling of scrubbers and downstream equipment. This is in particular the case when limestone or lime is used in the acid scrubber and soda in the alkaline scrubber since the mixture of calcium chloride, which results from the neutralization of hydrochloric acid, and sodium sulfate, which results from the neutralization of sulfur dioxide, will give gypsum, poorly soluble and which precipitates.
    Even in the case where the precipitation of this gypsum would be done in a more or less controlled manner, that is to say not anarchic, the gypsum ends up with the water treatment mentioned above: thus this gypsum is found mixed metal hydroxide sludge and thus increase its volume. However, as this sludge must generally be placed in controlled landfills, this significantly increases the cost.
    In addition, the precipitation takes place under conditions where the heavy metals are still in solution, which means that the gypsum itself can only be of poor quality, in the sense that it contains too much heavy metals, which makes it unsuitable for any valuation.
    Finally there are situations where, on the same industrial site, several trains of scrubbers are present, using different reagents, for example because fumes respectively from different processes must be purified. Again, at some point, the various purges from the scrubbers present are mixed and are therefore likely to cause precipitation which is both uneconomic and a source of trouble for washing and water treatment.
    The object of the present invention is to provide a purification process and installation, which are more efficient, in particular with regard to the fouling of purification materials, and more economical, in particular by potential downstream recovery.
    To this end, the invention relates to a process for the treatment of wet combustion fumes, to purify them from sulfur dioxide, hydrochloric acid and the heavy metals which they contain, in which
    - the fumes to be treated are sent to an acid scrubber, which is supplied with lime or limestone, then to an alkaline scrubber, which is supplied with soda,
    - the purge of the acid scrubber is sent to a precipitation-crystallization unit after being purified by a first treatment of water,
    - the purge of the alkaline scrubber is sent, separately from the purge of the acid scrubber, to the precipitation-crystallization unit,
    - in the crystallization precipitation unit (301), precipitated gypsum is formed by the reaction Ca ++ + SO4 -> Ca SO4 4-, with Ca ++ which is provided by the purge (4) of the acid scrubber (101 ) and SO4 which is supplied by the purge (7) of the alkaline washer (102),
    - the outlet of the precipitation-crystallization unit, containing precipitated gypsum, is admitted into a solid liquid separator to produce a flow of gypsum, containing less than 15% by weight of free water and intended to be recovered, and a flow residual liquids, and
    - 30 to 100% in flow, preferably 50 to 80% in flow, of the flow of residual liquids are purified by a second treatment of water to produce a brine intended to be recovered, the remainder of the flow of residual liquids being recycled to either of the acid and alkaline washers, and
    CH 706 405 B1
    - the residues resulting from the first and second water treatments are rich in metals and are evacuated, being likely to be recovered.
    The invention also relates to an installation for the treatment of wet combustion fumes, to purify them from sulfur dioxide, hydrochloric acid and the heavy metals which they contain, comprising:
    - an acid scrubber supplied with fumes to be treated and with lime or limestone,
    - an alkaline washer supplied with the fumes coming from the acid washer and with soda,
    - a first water treatment unit, supplied by the purge of the acid scrubber,
    - a precipitation-crystallization unit, which is supplied, separately, by the purge of the acid scrubber, purified by the first water treatment unit, and by the purge of the alkaline scrubber, and in which precipitated gypsum is formed by the reaction Ca ++ + SO4 -> Ca SO4 4, with Ca ++ which is provided by the purging of the acid scrubber and SO4 which is provided by the purging of the alkaline scrubber,
    a liquid-solid separator, fed by the outlet of the precipitation-crystallization unit, containing precipitated gypsum, and suitable for producing a gypsum flow, containing less than 15% of free water and intended to be recovered, and a flow of residual liquids,
    - a second water treatment unit, supplied with 30 to 100% flow, preferably 50 to 80% flow, of the flow of residual liquids, and suitable for producing brine intended to be recovered,
    means for recycling to one and / or the other of the acid and alkaline washers the remainder of the flow of residual liquids, not treated by the second water treatment unit, and
    - means for removing residues resulting from the first and second water treatments, which are rich in metals and likely to be recovered.
    Thus, the invention makes it possible to carry out controlled gypsum precipitation and under clean conditions so as to obtain separately:
    - a fairly pure gypsum, intended to be used,
    - a brine substantially free of heavy metals, which can also be recovered, and
    - a small quantity of metal residues leaving the two water treatments, such as metal hydroxide cakes, sludge, concentrates, etc., also recoverable by recovery of the metals they contain, in particular zinc.
    The invention makes it possible to generate separate and recoverable flows by each outgoing product, as well as to ensure operating conditions for the materials, in particular the scrubbers, sheltering them from potential precipitation.
    According to additional advantageous characteristics of the process and of the installation in accordance with the invention, taken in isolation or in any technically possible combination:
    - at least one stream containing sulfates, other than the purge of the alkaline scrubber, is also allowed in the precipitation-crystallization unit,
    - the fumes treated by the acid and alkaline scrubbers are fumes from incineration of garbage, while fumes from the incineration of sludge from water purification plants are treated at least by another alkaline scrubber whose purge constitutes said at least one stream containing sulfates,
    - the second water treatment is more intensive than the first water treatment,
    - the remainder of the flow of residual liquids is sent to the acid scrubber,
    - an acid flow, in particular hydrochloric acid or sulfuric acid, is also introduced into the precipitation-crystallization unit,
    - the precipitation-crystallization unit comprises a crystallizer or a stirred tank,
    - the precipitation-crystallization unit comprises hydrocyclones,
    - the liquid-solid separator consists of a belt filter or a centrifuge.
    The invention will be better understood on reading the description which follows, given solely by way of example and made with reference to the drawings in which:
    fig. 1 is a diagram of an installation in accordance with the invention, implementing a process in accordance with the invention; and fig. 2 is a view similar to FIG. 1, illustrating a variant of the installation and the method in accordance with the invention.
    In the installation shown in fig. 1, fumes to be purified 1 pass through an acid scrubber 101, using lime or limestone neutralization reagent, then a second alkaline scrubber 102, using sodium hydroxide as neutralizing agent. The fumes leaving the acid washer 101 and entering the alkaline washer are referenced 2. Each washer 101, 102 is generally provided with a supply of fresh water, not shown, which makes it possible, among other things, to compensate for evaporations of water in the scrubbers.
    The purified fumes 3, leaving the downstream alkaline washer 102, are evacuated, for example via a chimney and a draft fan, or else are subjected to an additional treatment, which is not the subject of the invention and what is therefore not shown in FIG. 1.
    CH 706 405 B1 The liquid purge 4 of the acid washer 101 is sent to a water treatment unit 201 in which the purge 4 is freed from at least 90% by weight of heavy metals, such as lead, zinc or cadmium. The water treatment implemented in unit 201 is known in itself and is not the subject of the invention. A stream 5, consisting, inter alia, of hydroxide sludges or hydroxide cakes or of metal concentrates in the case where the water treatment is of the ion exchange resin type, comes from the water treatment unit 201 and discharged: this product flow 5 can be recovered because it is rich in metals. The main outlet of the water treatment unit 201 is a liquid stream 6 consisting of the purge of the acid scrubber 101, freed from heavy metals by the water treatment implemented in the unit 201. This stream 6 is sent to a precipitation-crystallization unit 301 detailed below.
    The unit 301 also receives the purge 7 of the alkaline washer 102: as shown in FIG. 1, this purge 7 is sent from the alkaline washer 102 to the precipitation-crystallization unit 301 separately from the purge stream coming from the acid washer 101, and this directly, that is to say without treatment significantly modifying the composition of this purge 7.
    The precipitation-crystallization unit 301 makes it possible to produce precipitation controlled by crystallization of the gypsum which will form there. More precisely, insofar as, in this unit 301, the treated purge 6 coming from the acid scrubber 101, which mainly contains calcium chloride in solution produced by the neutralization reaction between hydrochloric acid and the neutralization reagent used, for example limestone or lime, is mixed with the purge 7 of the alkaline washer 101 containing sulfates, which are produced by the neutralization reaction between the sulfur dioxide and the neutralizing agent used, for example soda, gypsum is formed by the reaction:
    Ca ++ (provided by 4) + SO 4 (provided by 7) -> Ca SO 4 4- (in hydrated form).
    Optionally, an acid flow 8, which may be sulfuric acid or hydrochloric acid, is also introduced into the precipitation-crystallization unit 301: it can indeed be beneficial, in particular for the quality of the gypsum crystals obtained, to carry out the precipitation-crystallization reaction of the gypsum under slightly acidic pH conditions.
    The precipitation-crystallization unit 301 is of a technology known per se. In particular, this unit 301 can consist of a stirred tank or of a crystallizer and of auxiliary units such as pumps and hydrocyclones intended to maintain the nucleation nuclei in this unit 301.
    The main output 9 of the precipitation-crystallization unit 301, which contains the precipitated gypsum produced, is directed to a liquid-solid separator 302. This liquid-solid separator 302, which is for example a band filter or a centrifuge is also supplied with water 11 which, in the separator 302, washes the gypsum to provide it with characteristics making it recoverable. This separator 302 then makes it possible to produce a flow of gypsum 10, which contains less than 15% by weight of free water and whose gypsum is purified and white. For example, the purity of the gypsum contained in this stream 10 is such that this stream contains at least 95% by weight of pure gypsum, as well as, at most, 0.1% by weight of magnesium, 0.01% by weight of chlorine, 0.5% by weight of calcium sulfite (CaSO 3 ), 0.15% by weight of ferric oxide (Fe 2 O 3 ), 2.5% by weight of silica (SiO 3 ) and 0.3% by weight of alumina (AI 2 O 3 ).
    The residual liquids leaving the liquid-solid separator 302 form a flow 12 of which at least part, or even all, forms a flow 13 sent to a water treatment unit 401, which is different from the unit 201 but which has the same intrinsic action as the latter, namely to rid the incoming flow of its heavy metals. In practice, the water treatment unit 401 is based on a technology known per se. According to the invention, the flow 13 sent to the water treatment unit 401 represents between 30 and 100% in flow of the flow 12, preferably between 50 and 80% in flow of this flow 12.
    Under the action of the water treatment implemented in this unit 401, the flow 13 is purified until producing a potentially recoverable brine 15. In particular, this brine 15 essentially consists of sodium chloride in aqueous solution. The residues, resulting from the water treatment implemented in unit 401, form sludge or a cake or a concentrate or the like 16, which are rich in metals and which are removed from the installation for potential recovery.
    It will be noted that, according to an advantageous arrangement of the invention, the water treatment, implemented in unit 201, does not have to be as intensive as that implemented in unit 401, in the sense that, unlike the brine 15 intended to be recovered, the flow 6 leaving the unit 201 necessarily undergoes, downstream of this unit 201, additional treatments, as described above. In practice, this amounts to saying that the unit 401 is designed to carry out a complete water treatment while the unit 201 is only designed to carry out a partial water treatment.
    In the case where only part of the flow of residual liquids 12 is sent to the water treatment unit 401, that is to say in the case where the flow 13 is not equal to 100 % of flow 12, the residue 14 of the flow of residual liquids 12 is recycled in the installation, being returned to one and / or the other of the washers 101 and 102, preferably to the acid washer 101 as shown in the fig. 1. The recycling of the residue 14 makes it possible to reduce the quantity of fresh water overall consumed for washing the fumes.
    Thus, as will be understood from reading the above, the invention consists essentially of separating the purges 4 and 7 from the scrubbers 101 and 102, extracting the heavy metals from the purge 4 of the acid scrubber 101 and then mix
    CH 706 405 B1 the latter with the purge 7 of the alkaline washer 102, containing sulfates, under controlled conditions to precipitate-crystallize gypsum. In this way and according to the invention, we obtain:
    - a gypsum stream 10 intended to be recovered,
    a brine 15 essentially consisting of sodium chloride in water, potentially recoverable, and
    - flows 5 and 16 of the remainders of the two water treatments, which are in limited quantities since they no longer contain gypsum and which are rich in metals which also makes them susceptible to being recovered.
    As will also be understood, by separating one from the other the purges 4 and 7, one avoids any problem of uncontrolled precipitation in the scrubbers 101 and 102, as well as immediately downstream of these scrubbers.
    Note also that, according to an advantageous characteristic of the invention, the precipitation-crystallization which takes place in the unit 301, is done from solutions which contain only very little heavy metals, in particular because the water treatment implemented in unit 201 treated the purge 4 which is the main source of these metals. This ensures high purity of the gypsum which forms in the precipitation-crystallization unit 301.
    The invention is also of particular interest in cases where, on the same industrial site, there are several streams containing sulfates. This is particularly the case for incineration sites on which one or more lines are dedicated to the incineration of waste or garbage, while one or more other lines are dedicated to the incineration of sludge from wastewater treatment plants. water purification: this typical case is illustrated in fig. 2.
    Indeed, in FIG. 2, the materials 101, 102, 201, 301, 302 and 401 are respectively identical to those described above with reference to FIG. 1 and perform the same respective functions. Thus, these materials 101, 102, 201, 301, 302 and 401 treat the fumes to be purified 1 which are, for example, waste incineration fumes. At the same time, fumes to be purified 1 'consisting of sludge incineration fumes from a water treatment plant, are treated by a dedicated line which, as shown in fig. 2, is separated from the washers 101 and 102. This dedicated line produces an effluent 17 rich in sulphates. Typically, this dedicated line comprises at least two washers 501 and 502, the washer 502 being an alkaline washer having captured the sulfur dioxide from the fumes 1 ′ and producing the stream 17. According to an advantageous characteristic of the invention, the rich stream 17 in sulphates feeds the precipitation-crystallization unit 301, which allows more gypsum to be produced there. Thus, an additional benefit is linked to the fact that, without this provision of the invention, flow 17 would have to be treated differently before it is released to the environment.
    权利要求:
    Claims (9)
    [1]
    claims
    1. Process for treating wet combustion fumes, to purify them from sulfur dioxide, hydrochloric acid and the heavy metals which they contain, in which:
    - the fumes to be treated (1) are sent to an acid scrubber (101), which is fed with lime or limestone, then to an alkaline scrubber (102), which is fed with soda,
    - the purge (4) of the acid scrubber (101) is sent to a precipitation-crystallization unit (301) after having been purified by a first treatment of water,
    the purge (7) of the alkaline scrubber (102) is sent, separately from the purge of the acid scrubber, to the precipitation-crystallization unit (301),
    -in the precipitation-crystallization unit (301), precipitated gypsum is formed by the reaction Ca ++ + SO4 Ca SO41, with Ca ++ which is provided by the purge (4) of the acid scrubber (101) and SO4 which is supplied by the purge (7) of the alkaline washer (102),
    - the outlet (9) of the precipitation-crystallization unit (301), containing the precipitated gypsum, is admitted into a liquid-solid separator (302) to produce a flow of gypsum (10), containing less than 15% in weight of free water intended to be recovered, and a flow of residual liquids (12),
    - 30 to 100% in flow, preferably 50 to 80% in flow, of the flow of residual liquids (12) are purified by a second water treatment to produce a brine (15) intended to be recovered, the remainder (14 ) of the residual liquid stream being recycled to one and / or the other of the acid (101) and alkaline (102) washers, and
    - the residues (5, 16) resulting from the first and second water treatments are rich in metals and are evacuated, being likely to be recovered.
    [2]
    2. The method of claim 1, wherein at least one stream (17) containing sulfates, other than the purge (7) of the alkaline washer (102), is also admitted into the precipitation-crystallization unit (301).
    [3]
    3. The method of claim 2, wherein the fumes (1) treated by the acid washers (101) and alkaline (102) are waste incineration fumes, while fumes (1 ') incineration sludge from a water purification station is treated at least by another alkaline scrubber (502), the purging of which constitutes said at least one stream (17) containing sulfates.
    [4]
    4. Method according to any one of the preceding claims, in which the remainder (14) of the flow of residual liquids (12) is sent to the acid scrubber (101).
    [5]
    5. Method according to any one of the preceding claims, in which an acid stream (8), in particular hydrochloric acid or sulfuric acid, is also introduced into the precipitation-crystallization unit (301).
    CH 706 405 B1
    [6]
    6. Installation for the treatment of combustion smoke by the wet process, to purify it from sulfur dioxide, hydrochloric acid and the heavy metals which it contains, comprising:
    - an acid scrubber (101) supplied with fumes to be treated (1) and with lime or limestone,
    - an alkaline washer (102) supplied with the fumes (2) leaving the acid washer (101) and with soda,
    - a first water treatment unit (201), supplied by the purge (4) of the acid scrubber (101),
    - a precipitation-crystallization unit (301), which is supplied, separately, by the purge of the acid scrubber, purified by the first water treatment unit (201), and by the purge (7) of the alkaline scrubber (102), and in which precipitated gypsum is formed by the reaction Ca ++ + SO4 -> Ca SO4 4-, with Ca ++ which is provided by the purge (4) of the acid scrubber (101) and SO4 which is supplied by the purge (7) of the alkaline washer (102),
    - a liquid-solid separator (302), supplied by the outlet (9) of the precipitation-crystallization unit (301), containing precipitated gypsum, and suitable for producing a flow of gypsum (10), containing less than 15 % of free water intended to be recovered, and a flow of residual liquids (12),
    - a second water treatment unit (401), supplied with 30 to 100% in flow, preferably 50 to 80% in flow, of the flow of residual liquids (12), and adapted to produce a brine (15) intended to be valued,
    - Means for recycling to one and / or the other of the acid (101) and alkaline (102) washers the remainder (14) of the flow of residual liquids (12), not treated by the second treatment unit of water (401), and
    - means for removing residues (5, 16) resulting from the first and second water treatments, which are rich in metals and likely to be recovered.
    [7]
    7. Installation according to claim 6, wherein the precipitation-crystallization unit (301) comprises a crystallizer or a stirred tank.
    [8]
    8. Installation according to one of claims 6 or 7, wherein the precipitation-crystallization unit (301) comprises hydrocyclones.
    [9]
    9. Installation according to any one of claims 6 to 8, in which the liquid-solid separator (302) consists of a band filter or a centrifuge.
    CH 706 405 B1
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    同族专利:
    公开号 | 公开日
    FR2989285A1|2013-10-18|
    CH706405A2|2013-10-31|
    引用文献:
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    CN111088502A|2018-10-23|2020-05-01|南京化学工业园环保产业协同创新有限公司|Application method of cyclic regeneration type spraying agent|DE3920544C1|1989-02-28|1990-10-04|Mannesmann Ag, 4000 Duesseldorf, De|Flue gas purificn. system downstream of refuse incinerator - has acid treatment stage receiving sodium hydroxide to form pure sodium chloride which recycled to mixer stage|
    SE470565B|1993-01-21|1994-08-29|Flaekt Ab|Method and apparatus for purifying hydrocarbon and sulfur dioxide containing gases|
    SE502159C2|1993-12-22|1995-09-04|Flaekt Ab|Method and apparatus for making plaster of high purity|
    法律状态:
    2019-11-29| PL| Patent ceased|
    优先权:
    申请号 | 申请日 | 专利标题
    FR1253475A|FR2989285A1|2012-04-16|2012-04-16|Method for purification of flue gases by wet process in household refuse incineration factory, involves purifying flow of residual liquids by water treatment, and recycling remainder of flow of liquids towards acid and alkaline washers|
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