CN1126578C - 生活垃圾和/或工业废弃物焚烧烟气提纯残渣的处理方法 - Google Patents
生活垃圾和/或工业废弃物焚烧烟气提纯残渣的处理方法Info
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- CN1126578C CN1126578C CN98807192A CN98807192A CN1126578C CN 1126578 C CN1126578 C CN 1126578C CN 98807192 A CN98807192 A CN 98807192A CN 98807192 A CN98807192 A CN 98807192A CN 1126578 C CN1126578 C CN 1126578C
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- 239000003517 fume Substances 0.000 title abstract 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 239000012065 filter cake Substances 0.000 claims description 17
- 238000006386 neutralization reaction Methods 0.000 claims description 12
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- 239000003546 flue gas Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 238000003672 processing method Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 238000010612 desalination reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 238000005422 blasting Methods 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
本发明的方法包括如下步骤:A)通过足够量或稍微过量的碳酸钠(2)洗涤残渣(1、1’)脱除盐份,使包括硫酸盐在内的各种盐溶解并使可溶性钙沉淀,使pH值大于11,然后进行固/液分离,得到脱盐的滤饼(3);B)将由步骤A得到的滤饼(3)用必需量或稍微过量的碳酸钠浸滤,以便通过与滤饼中存在的或者如果需要被加入的石灰反应得到溶解两性金属所需的碱,得到大于12的pH值,通过固/液分离得到滤饼(6)和上清液(7),用二氧化碳(8)进行中和并过滤回收的溶液,一方面得到金属氢氧化物淤浆(11),另一方面得到碳酸钠水溶液(14),将此溶液循环到步骤B)本身使用,以及C)将步骤B得到的残渣(6、6’)中和到6.5~8.5的pH值。
Description
本发明涉及生活垃圾和/或工业废弃物焚烧烟气提纯过程产生的残渣的处理方法。
焚烧工厂处理生活垃圾时一方面产生炉渣,另一方面产生充满粉尘并含有有害气体的烟气。消除烟气的污染一般是通过石灰来实现的:在这里,氯化氢和含硫气体被俘获,转化为氯化钙和硫酸钙,而烟气中存在的重金属则被吸附在石灰颗粒的表面。在用石灰进行这样的处理以后,在过滤器出口得到的产物总体构成目前被排放或储存在符合国家标准、欧洲标准或国际标准的地方的残渣。
因此这些残渣含有与石灰反应产生的产物、被吸附的两性重金属、碳酸钙、石灰和由焚烧产生和在石灰上进行处理而捕获的惰性粉尘状产物(比如二氧化硅和氧化铝)。
由不同组分构成的残渣的组成显然与焚烧的垃圾和废弃物的种类以及使用的烟气处理方法的类型有关。
这些残渣根据污染情况被分成三类:
—不含有污染物的品种;
—含有有害或污染产物,但呈稳定状态的品种:它们对于外界环境没有任何危险;以及
—含有可能触及外部环境的有害元素的品种:它们占残渣重量大约2%。
因此本领域专业人员将会明白,最后这类残渣是潜在的污染源:它特别含有容易接近因而容易对外界环境产生污染的重金属,这就是目前规定在适当地方进行储存的原因。
因此,本发明的目的是提供生活垃圾和/或工业废弃物焚烧烟气提纯残渣的处理方法,该方法可以提取重金属和最大限度地回收反应物。
本发明的另一个目的是提供这样一种还能够分离在残渣中存在的各种元素,以便使其得到充分利用,并依照现行法规循环使用或将其除去的方法。
本发明另一个目的是提供一种此类能够利用例如从焚烧厂排放的二氧化碳气体的方法。
本发明的又一个目的是提供这样一种能够以尽可能低的成本使得到的产物被充分利用的方法。
通过一种生活垃圾和/或工业废弃物焚烧烟气提纯残渣的处理方法实现了这些目的以及其它目的,按照本发明,该方法的特征在于包括如下步骤:
A-通过足够量或稍微过量的碳酸钠洗涤残渣脱除盐份,使包括硫酸盐在内的各种盐溶解,并使可溶性钙沉淀、使pH值大于11,然后进行固/液分离,得到脱盐的滤饼;
B-将由步骤A得到的这些滤饼用必需量和稍微过量的碳酸钠浸滤,通过与在滤饼中存在的或者如果需要被加入的石灰反应获得溶解两性金属所需的碱,得到大约14的pH值,通过固/液分离得到滤饼和上清液,用二氧化碳中和上清液并过滤回收的溶液,一方面得到金属氢氧化物的淤浆,另一方面得到碳酸钠水溶液,将此溶液循环到步骤B本身使用,以及
C-将步骤B得到的残渣中和到6.5~8.5的pH值。
优选在步骤A以前进行一个步骤D,即用水对残渣进行预洗涤,以除去可溶性钙盐,比如特别是氯化钙。
优选用鼓入二氧化碳的方法中和自步骤A得到的溶液,通过固/液分离回收金属氢氧化物淤浆和被中和的溶液。对金属氢氧化物淤浆和被中和的溶液进行同样的操作。对步骤D的溶液也进行同样的操作。将中和的溶液混合并过滤,得到由氯化钙和氯化钠溶液构成的上清液和硫酸钙沉淀,即石膏。
在步骤B和步骤C之间优选加入一个步骤E,即洗涤来自步骤B的滤饼,以最大限度地除去碳酸钠和残留在间质液体中的金属。优选在洗涤溶液中通入二氧化碳进行处理,直至pH值接近11为止。该碳酸钠溶液优选循环到步骤A中使用。
至于中和由步骤B或步骤E得到的残渣的步骤C,通过通入二氧化碳来进行,以使碳酸钙沉淀,从而得到提纯的残渣。
下面的叙述没有任何限定的特征,应该参照附图阅读,图中:
—图1是相继的主要步骤的示意图,这些步骤构成了本发明生活垃圾和/或工业废弃物焚烧烟气提纯残渣的处理方法;以及
—图2是此方法优选实施方案的相继步骤的示意图。
这样,由图1可以看出,本发明的生活垃圾与工业废弃物焚烧烟气提纯残渣的处理方法包括至少三个步骤。
在第一步或步骤A中,通过用碳酸钠2洗涤使提纯残渣1脱除盐份。碳酸钠的用量至少是溶解包括硫酸盐在内的各种盐所必需的量,这就是说至少是可以使可溶性钙沉淀下来的化学计量,因此pH值大于11,优选大于12。然后,通过比如过滤进行固/液分离,一方面得到脱盐的滤饼3,另一方面得到富盐的溶液4。
通过二氧化碳8鼓泡,中和由步骤A得到的富盐溶液4(步骤G):这时的pH值为8.5~9.5,优选9~9.2。通过固/液分离比如过滤得到金属氢氧化物淤浆11和中和溶液15。
在第二步即步骤B中,由步骤A得到的脱盐滤饼3被所需量或稍微过量的碳酸钠浸滤,得到为溶解两性金属如镉(Cd)、铅(Pb)和锌(Zn)所需的碱性,这就是说pH值至少大于12,甚至大约是14。该碱性通过碳酸钠与在残渣中存在的和/或如果需要时加入的石灰5反应得到。然后,进行固/液分离,一方面得到脱除了污染的残渣滤饼6,另一方面得到含有两性金属的上清液7。
在步骤F用二氧化碳气体8中和此上清液7,这时pH值为11~11.5,优选等于11,过滤回收的溶液,一方面得到金属氢氧化物淤浆11,另一方面得到碳酸钠水溶液4,可以将其循环到步骤B。
在第三步或步骤C,由步骤B得到的除污残渣滤饼6被通入的二氧化碳8中和,以使可能以碳酸钙形式存在的残留石灰沉淀,pH值为6.5~8.5,优选等于7.5,然后进行固/液分离比如过滤,一方面得到提纯的残渣9,另一方面得到碳酸氢钠溶液12。
在步骤C后回收的提纯残渣9可以被用作填料,或者加入到焚烧炉中,转化为炉渣:因此它们都可以得到利用。
按照图2所示方法的优选实施模式,与在前面参考图1所述方法相比,该方法还包括一些附加步骤。
因此,优选在步骤A之前,将焚烧烟气的提纯残渣用水洗涤(步骤D),视具体情况而定加入碳酸钠,如在步骤C得到的溶液12。通过固/液分离,一方面得到脱除了氯化物的残渣滤饼1’,另一方面得到氯化物溶液13。在步骤G’中,通过通入二氧化碳气体8中和此溶液,这时pH值为8.5~9.5,优选9~9.2,通过固/液分离比如过滤,一方面回收金属氢氧化物淤浆11,另一方面得到中和溶液14。
由步骤G’得到的被中和溶液14与由步骤G得到的溶液15混合,然后进行固/液分离比如过滤,得到由氯化钙和氯化钠浓溶液构成的上清液16,以及硫酸钙的沉淀即石膏17。
在步骤E中,由步骤B得到的脱除污染的残渣滤饼6可以在过滤时被水洗涤,以最大限度地除去碳酸钠和可能残留在间质液体中的金属。然后通过通入二氧化碳气体8处理洗涤溶液18,直至得到接近11的pH值(步骤1)为止。如此中和的含有碳酸钠和金属的溶液被循环到步骤A中。然后在步骤C提纯脱除了污染的残渣滤饼6’。
在下面的表中,指出了经过本发明方法处理并且由具有不同组成的各种焚烧残渣得到的提纯残渣的组成。
表
提纯残渣 | 组成%(重量) | |||||||
Na | K | Ca | Cl | SO4 | Pb | Zn | ||
干燥 | 提纯前 | 3 | 4.6 | 36 | 22.4 | 1.5 | 0.04 | 0.27 |
提纯后 | 0 | 0 | 53.75 | 0 | 0 | 0.007 | 0.088 | |
半潮湿 | 提纯前 | 0.8 | 1.6 | 16.8 | 5 | 4.4 | 0.17 | 0.57 |
提纯后 | 0 | 0 | 19.46 | 0 | 0 | 0.05 | 0.22 | |
潮湿 | 提纯前 | 0 | 0 | 10.8 | 0.64 | 4.95 | 0.4 | 1.26 |
提纯后 | 0 | 0 | 18.33 | 0 | 0 | 0.12 | 0.34 |
我们将注意到,在处理过的残渣中,重金属的含量低于目前的允许值。
Claims (9)
1.生活垃圾和/或工业废弃物焚烧烟气提纯残渣的处理方法,其特征在于包括如下步骤:
A-通过足够量或稍微过量的碳酸钠(2)洗涤残渣(1、1’)脱除盐份,使包括硫酸盐在内的各种盐溶解并使可溶性钙沉淀,使pH值大于11,然后进行固/液分离,得到脱盐的滤饼(3);
B-将由步骤A得到的滤饼(3)用必需量或稍微过量的碳酸钠浸滤,以便通过与滤饼中存在的或者如果需要被加入的石灰反应得到溶解两性金属所需的碱,得到大于12的pH值,通过固/液分离得到滤饼(6)和上清液(7),用二氧化碳(8)进行中和并过滤回收的溶液,一方面得到金属氢氧化物的淤浆(11),另一方面得到碳酸钠水溶液(14),将此溶液循环到步骤B本身使用,以及
C-将步骤B得到的残渣(6、6’)中和到6.5~8.5的pH值。
2.权利要求1的方法,其特征在于在步骤A之前进行步骤D,用水预先洗涤该残渣,以除去可溶性钙盐。
3.权利要求1的方法,其特征在于通过鼓入二氧化碳气体(8)中和由步骤A得到的溶液,并通过固/液分离回收金属氢氧化物淤浆(11)和被中和的溶液(15)。
4.权利要求2的方法,其特征在于通过鼓入二氧化碳气体(8)中和由步骤D得到的溶液,并通过固/液分离回收金属氢氧化物淤浆(11)和中和的溶液(14)。
5.权利要求3的方法,其特征在于,将中和过的溶液(14、15)混合并过滤,以得到由氯化钙和氯化钠溶液构成的上清液(16)和硫酸钙沉淀即石膏(17)。
6.权利要求1的方法,其特征在于在步骤B和C之间进行步骤E,即洗涤由步骤B得到的滤饼(6),以除去碳酸钠和在间质液体中残留的金属,并回收洗涤液(18)。
7.权利要求6的方法,其特征在于通过通入二氧化碳处理中和后的溶液直至pH值为11为止,以得到碳酸钠溶液。
8.权利要求7的方法,其特征在于该碳酸钠溶液被循环到步骤A。
9.权利要求1~6中任一项的方法,其特征在于通过通入二氧化碳气体(8)中和由步骤B或E得到的残渣(6、6’),使碳酸钙(10)沉淀,以得到提纯的残渣(9)。
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FR9707219A FR2764531B1 (fr) | 1997-06-11 | 1997-06-11 | Procede pour traiter les residus d'epuration des fumees d'incineration d'ordures menageres et/ou de dechets industriels |
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JP4549579B2 (ja) * | 2001-06-21 | 2010-09-22 | 太平洋セメント株式会社 | 塩素分および鉛分の含有量が高い廃棄物の処理方法 |
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CN100427179C (zh) * | 2006-12-01 | 2008-10-22 | 清华大学 | 一种利用垃圾焚烧灰渣固定co2的方法 |
FR2915692B1 (fr) | 2007-05-04 | 2009-07-17 | G A C E Services En Administra | Traitement pour stabiliser les refiom et autres dechets analogues |
FR2915691B3 (fr) * | 2007-05-04 | 2009-03-27 | G A C E Services En Administra | Traitement de stabilisation des refiom et autres dechets industriels analogues |
WO2014088413A2 (en) * | 2012-12-06 | 2014-06-12 | Tauw B.V. | Process for the treatment of solid alkaline residue comprising calcium, heavy metals and sulphate |
CN104445552B (zh) * | 2014-11-19 | 2016-08-24 | 沈阳航空航天大学 | 去除从渗滤液中提取的腐植酸中重金属的装置和方法 |
WO2020076778A1 (en) * | 2018-10-08 | 2020-04-16 | Marsulex Environmental Technologies Corporation | Systems and methods for producing potassium sulfate |
WO2020220117A1 (en) * | 2019-04-29 | 2020-11-05 | Fpinnovations | Process to recover alkali from a metal oxide/hydroxide containing material |
FR3120319B1 (fr) | 2021-03-08 | 2023-02-17 | Marcus Invest | Procede de traitement de dechets industriels mineraux pour obtenir un vitrifiat ayant des proprietes hydrauliques, liant hydraulique routier obtenu |
CN113750961B (zh) * | 2021-08-30 | 2023-07-25 | 河北工业大学 | 一种二氧化碳吸附剂及其制备方法 |
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CZ294643B6 (cs) | 2005-02-16 |
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