JP4727969B2 - Waste disposal method - Google Patents
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- JP4727969B2 JP4727969B2 JP2004310370A JP2004310370A JP4727969B2 JP 4727969 B2 JP4727969 B2 JP 4727969B2 JP 2004310370 A JP2004310370 A JP 2004310370A JP 2004310370 A JP2004310370 A JP 2004310370A JP 4727969 B2 JP4727969 B2 JP 4727969B2
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- 239000002699 waste material Substances 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 21
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical compound O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 18
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 150000002611 lead compounds Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000010802 sludge Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001844 chromium Chemical class 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011260 aqueous acid Substances 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Treatment Of Sludge (AREA)
- Fire-Extinguishing Compositions (AREA)
- Processing Of Solid Wastes (AREA)
Description
本発明は、廃棄物処理方法に関する。 The present invention relates to a waste treatment method.
従来より重金属を含む有害スラッジまたはその焼却灰あるいは集塵装置等によって集められたじん灰等の汚泥物あるいは粉状物は、有機物あるいは粉状コークスを加えて熱処理して、埋め立て処分されている。
例えば、重金属を含むスラッジまたはその焼却灰あるいは集じん装置等によって集められたじん灰等に有機物または粉状コークスを加え、非酸化性雰囲気で700〜1300℃の温度で熱処理し、カドミウム、亜鉛、鉛を揮散させ捕集回収することを特徴とする重金属を含むスラッジ等の処理方法が挙げられる。（例えば特許文献１参照）
また、例えば重金属を含むスラッジあるいは集じんダスト等を汚泥物または粉状物を、塩化ビニール樹脂を含む廃合成樹脂と共に焼却し、スラッジ等に含まれる重金属を塩化物として揮散させ捕集回収する処理方法が挙げられる。（例えば特許文献２参照）
その他、クロム酸鉛スラッジは、そのままあるいは無害化処理を施して、産業廃棄物の埋立処分基準にしたがって埋立処分されている。
For example, sludge containing heavy metal or its incinerated ash or dust ash collected by dust collector etc. is added organic matter or powdered coke, heat treated at a temperature of 700-1300 ° C. in a non-oxidizing atmosphere, cadmium, zinc, A method for treating sludge containing heavy metals, characterized by volatilizing and collecting lead, can be mentioned. (For example, see Patent Document 1)
In addition, for example, sludge or dust collection dust containing heavy metals is incinerated with sludge or powdered materials together with waste synthetic resin containing vinyl chloride resin, and the heavy metals contained in sludge etc. are volatilized as chlorides and collected and recovered. A method is mentioned. (For example, see Patent Document 2)
In addition, lead chromate sludge is landfilled according to the industrial waste landfill disposal standards as it is or after being detoxified.
従来法の内、熱処理する方法は、熱処理設備、揮散物質回収設備、排ガス処理設備等の多くの設備が必要となる上、燃料等の多大なエネルギーを必要とする。更に、最終的に埋立処分が必要な廃棄物が発生する。
また、そのままあるいは無害化処理を施して埋め立て処分する方法は、クロム酸鉛が水に対して難溶性の化合物であることから最も簡便な処分方法ではあるが、クロム酸鉛が６価クロム化合物であることに変わりなく、酸性あるいはアルカリ性の環境中では溶解して６価クロムと鉛を溶出する危険性を有している。又、近年、埋め立て処分は、用地の確保等が困難の理由で処分が出来にくく、これに代わる新しい処理方法の開発が望まれている。
Of the conventional methods, the heat treatment method requires many facilities such as a heat treatment facility, a volatile substance recovery facility, and an exhaust gas treatment facility, and also requires a large amount of energy such as fuel. In addition, waste that eventually needs to be disposed of is generated.
In addition, the landfill disposal method with or without detoxification is the simplest disposal method because lead chromate is a compound that is sparingly soluble in water, but lead chromate is a hexavalent chromium compound. There is no change, and there is a risk of dissolving and dissolving hexavalent chromium and lead in an acidic or alkaline environment. In recent years, landfill disposal is difficult to dispose of because of difficulty in securing land, and development of a new treatment method that replaces this has been desired.
従って本発明の目的は、熱処理する方法のような多大な設備とエネルギーを使わず、クロム酸鉛廃棄物を埋め立て処分することなく、クロムと鉛を分離してリサイクル可能にする処理方法及びリサイクル可能な鉛化合物を提供することにある。 Accordingly, an object of the present invention is to use a processing method and recyclable which can separate and recycle chromium and lead without using a large amount of equipment and energy as in the heat treatment method and without landfilling lead chromate waste. It is to provide a lead compound.
本発明は、クロム酸鉛（PbCrO 4 ）を含む廃棄物を硫酸水溶液中で加熱処理して、該廃棄物中に含まれるクロムを水溶性のクロム酸（H 2 CrO 4 ）にし、また鉛を難溶性の硫酸鉛に転換して、反応終了後の酸性スラリーを中和することなく、該スラリー中に溶解した該クロム酸と該難溶性の硫酸鉛を固液分離することを特徴とする廃棄物処理方法を提供するものである。
In the present invention, waste containing lead chromate (PbCrO 4 ) is heat-treated in a sulfuric acid aqueous solution to convert chromium contained in the waste into water-soluble chromic acid (H 2 CrO 4 ). Disposal characterized in that the chromic acid dissolved in the slurry and the hardly soluble lead sulfate are separated into solid and liquid without neutralizing the acidic slurry after completion of the reaction by converting into the hardly soluble lead sulfate. An object processing method is provided.
本発明で得られたクロム酸と鉛化合物は、それぞれクロム塩製造原料、鉛原料として有効利用が可能であり、実質的に埋め立て処分が不要となる。 The chromic acid and the lead compound obtained in the present invention can be effectively used as a chromium salt production raw material and a lead raw material, respectively, and substantially do not require landfill disposal.
以下、本発明の好適な廃棄物処理方法について説明する。
本発明の廃棄物処理方法は、クロム酸鉛を含む廃棄物を酸性水溶液中で加熱処理して、該廃棄物中に含まれるクロムを水溶性のクロム酸にし、また鉛を難溶性の鉛化合物に転換し固液分離することによって特徴付けられる。
ここでいう難溶性の鉛化合物とは、硫酸鉛である。
本発明のクロム酸鉛を含む廃棄物は、ろ過ケーキ状で供給されてもスラリーとして供給されてもかまわない。
つまり、廃棄物中にあらかじめクロム酸が存在しても処理が進行することを意味している。これは、強酸性のクロム酸を含む廃棄物のスラリーを厳密にろ過および洗浄を要しないことから、設備的且つ操作的に有利となる。なお、廃棄物のスラリーとして供給される場合は、必要に応じて沈降濃縮することが望ましい。
Hereinafter, a preferred waste treatment method of the present invention will be described.
In the waste treatment method of the present invention, a waste containing lead chromate is heat-treated in an acidic aqueous solution to convert the chromium contained in the waste into water-soluble chromic acid, and lead is a poorly soluble lead compound. And is characterized by solid-liquid separation.
The poorly soluble lead compound here is lead sulfate.
The waste containing lead chromate of the present invention may be supplied as a filter cake or as a slurry.
In other words, the treatment proceeds even if chromic acid is present in the waste in advance. This is advantageous in terms of equipment and operation because the slurry of waste containing strongly acidic chromic acid does not require strict filtration and washing. In addition, when supplying as a slurry of a waste, it is desirable to carry out sedimentation concentration as needed.
本発明の廃棄物処理方法における酸性水溶液としては、塩酸または硫酸を選択できるが、硫酸を選択する。その理由としては、クロム酸を含む廃棄物をクロム塩製造原料として利用する場合、塩素を含有するとクロム塩製造工程において有毒な塩化クロミルを生成する可能性があることや塩化鉛は硫酸鉛と比較して溶解度が大きいためクロム塩製造工程に鉛が混入してしまうためである。更に、塩化鉛を鉛原料として利用する場合、塩素ガスが発生して設備の腐食を招く恐れがあるためである。 The acidic aqueous solution in the waste processing method of the present invention can be selected hydrochloric acid or sulfuric acid, select the sulfuric acid. The reason for this is that when waste containing chromic acid is used as a raw material for producing chromium salts, the inclusion of chlorine may produce toxic chromyl chloride in the chromium salt production process, and lead chloride is compared to lead sulfate. This is because lead is mixed into the chromium salt manufacturing process because of its high solubility. Furthermore, when lead chloride is used as a lead raw material, chlorine gas is generated, which may cause corrosion of equipment.
本発明の廃棄物の処理方法における酸として硫酸を使用した場合の反応式は以下の通りである。
PbCrO4 ＋ H2SO4 → PbSO4 ＋ H2CrO4
The reaction formula when sulfuric acid is used as the acid in the waste treatment method of the present invention is as follows.
PbCrO 4 + H 2 SO 4 → PbSO 4 + H 2 CrO 4
前記の反応式に示すように、廃棄物中に含まれるクロム酸鉛を硫酸鉛に転換するのに要する硫酸の理論量（化学量論量）はクロム酸鉛１モルに対して硫酸１モルであるが、クロム酸鉛の全量を硫酸鉛に転換するためには、実質的にクロム酸鉛１モルに対して硫酸６モル以上（化学量論量の６倍以上）が必要である。好ましくは、限りなく化学量論量に近づけるべきである。
その理由としては、過剰の硫酸は反応に関与しないうえ、分離母液を中和する際に余分なアルカリ剤を消費してしまうためである。ただし、仕込計量設備の能力に応じてその過剰量を決定すればよく、必ずしも無駄に精度の高い仕込計量設備を必要とするものではない。
As shown in the above reaction formula, the theoretical amount (stoichiometric amount) of sulfuric acid required to convert lead chromate contained in waste into lead sulfate is 1 mole of sulfuric acid per mole of lead chromate. However, in order to convert the entire amount of lead chromate to lead sulfate, it is necessary to substantially have 6 moles or more (6 times or more the stoichiometric amount) of sulfuric acid per mole of lead chromate. Preferably, it should be as close to the stoichiometric amount as possible.
The reason is that excess sulfuric acid does not participate in the reaction and consumes an excess alkali agent when neutralizing the separated mother liquor. However, it is only necessary to determine the excess amount according to the capacity of the preparation weighing equipment, and it does not necessarily require useless high precision preparation measurement equipment.
本発明の廃棄物処理方法における添加順序は、クロム酸を含む廃棄物に酸を添加してもよく、酸水溶液に廃棄物を添加してもよい。つまり、添加終了後にクロム酸鉛と必要量の酸が存在していればよく、添加順序を限定するものではない。 As for the order of addition in the waste treatment method of the present invention, an acid may be added to a waste containing chromic acid, or a waste may be added to an aqueous acid solution. That is, it is sufficient that lead chromate and a necessary amount of acid exist after the addition is completed, and the order of addition is not limited.
本発明の廃棄物処理方法における加熱処理温度は４０℃以上であるが、好ましくは４０℃以上６０℃以下である。その理由としては、４０℃以下では反応が進まないかあるいは反応速度が著しく遅いので工業的に有利でないためである。また、６０℃以上では加熱のための余分なエネルギーを消費してしまうためである。ただし、酸の希釈または添加により熱が発生する場合は、６０℃以下に限定するものではない。 Although the heat processing temperature in the waste processing method of this invention is 40 degreeC or more, Preferably it is 40 degreeC or more and 60 degrees C or less. The reason is that the reaction does not proceed below 40 ° C. or the reaction rate is remarkably slow, which is not industrially advantageous. Moreover, it is because the excess energy for a heating will be consumed at 60 degreeC or more. However, when heat is generated by dilution or addition of acid, it is not limited to 60 ° C. or less.
本発明の廃棄物の処理方法は、反応終了後、中和することなく酸性スラリーで固液分離することによっても特徴付けられる。反応生成物の鉛化合物を含んだまま中和処理すると、鉛化合物が部分的にクロム酸鉛に戻ってしまうためである。分離母液ならびに鉛化合物の中和が必要な場合は、分離した後で別々に中和すべきである。 The waste treatment method of the present invention is also characterized by solid-liquid separation with an acidic slurry without neutralization after completion of the reaction. This is because the lead compound partially returns to lead chromate when the neutralization treatment is performed while containing the lead compound of the reaction product. If separation mother liquor and lead compounds need to be neutralized, they should be neutralized separately after separation.
本発明の鉛化合物は、クロムの含有量が低レベルであることによって特徴付けられる。詳細には、本発明の鉛化合物は、クロムの含有量が乾燥物状態で１重量％以下という低レベルのものである。本発明者の検討の結果、クロム含有量が１重量％以下である本発明の鉛化合物は、鉛原料としてリサイクル可能であることが判明した。 The lead compounds of the present invention are characterized by a low level of chromium content. Specifically, the lead compound of the present invention has a low chromium content of 1% by weight or less in a dry product state. As a result of the study by the present inventors, it has been found that the lead compound of the present invention having a chromium content of 1% by weight or less can be recycled as a lead raw material.
以下に実施例を挙げて本発明を具体的に説明する。特に断らない限り「％」は「重量％」を意味する。 The present invention will be specifically described below with reference to examples. Unless otherwise specified, “%” means “% by weight”.
〔実施例１〕
５００ｍｌガラス製ビーカーに、水を２１０．２ｇ入れ、更に試薬の９５％硫酸４０．１ｇを投入し、充分撹拌して硫酸水溶液を調整した。クロム酸鉛としてはクロムめっき業者Ａから入手した表１に示す組成（乾燥物）のクロム酸鉛廃棄物２２．５ｇを用いた。
[Example 1]
In a 500 ml glass beaker, 210.2 g of water was added, and further 40.1 g of 95% sulfuric acid as a reagent was added and stirred sufficiently to prepare an aqueous sulfuric acid solution. As the lead chromate, 22.5 g of lead chromate waste obtained from the chromium plating company A and having the composition (dried material) shown in Table 1 was used.
硫酸水溶液をヒーターで加熱し、液温が４７℃となったところでクロム酸鉛を手動で添加した。添加に要した時間は３０分である。添加終了時の液温は５０℃で、この温度で６０分間熟成した。熟成終了後、９ｃｍφのブフナー式真空ろ過器で固液分離し、分離母液２７７．1ｇ並びに結晶１９．２ｇを回収した。得られた結晶はＸ線回折にてＰｂＳＯ4であることが確認された。得られた分離母液と結晶の組成は表２の通りであった。 The sulfuric acid aqueous solution was heated with a heater, and when the liquid temperature reached 47 ° C., lead chromate was added manually. The time required for the addition is 30 minutes. The liquid temperature at the end of the addition was 50 ° C., and aging was carried out at this temperature for 60 minutes. After completion of aging, solid-liquid separation was performed with a 9 cmφ Buchner vacuum filter, and 277.1 g of the separated mother liquor and 19.2 g of crystals were recovered. The obtained crystal was confirmed to be PbSO 4 by X-ray diffraction. The composition of the obtained separation mother liquor and crystals was as shown in Table 2.
〔実施例２〕
５００ｍｌガラス製ビーカーに、水を２１０．１ｇ入れ、更に表１に示す組成のクロム酸鉛廃棄物２２．５ｇを投入し、充分撹拌してクロム酸鉛スラリーを調整した。酸としては試薬の９５％硫酸４０．７ｇを用いた。
[Example 2]
In a 500 ml glass beaker, 210.1 g of water was added, and further 22.5 g of lead chromate waste having the composition shown in Table 1 was added and stirred sufficiently to prepare a lead chromate slurry. As the acid, 40.7 g of 95% sulfuric acid as a reagent was used.
クロム酸鉛スラリーの液温が２８℃で硫酸を手動で滴下して添加した。添加に要した時間は１０分である。必要に応じてヒーターで加熱して液温を５３℃前後に保ちながら６０分間以上熟成した。熟成終了後、９ｃｍφのブフナー式真空ろ過器で固液分離し、分離母液２６４．６ｇ並びに結晶１９．５ｇを回収した。得られた結晶はＸ線回折にてＰｂＳＯ4であることが確認された。得られた分離母液と結晶の組成は表３の通りであった。 Sulfuric acid was manually added dropwise at a liquid temperature of the lead chromate slurry of 28 ° C. The time required for the addition is 10 minutes. The mixture was aged for 60 minutes or more while maintaining the liquid temperature at around 53 ° C. by heating with a heater as necessary. After completion of aging, solid-liquid separation was performed with a 9 cmφ Buchner vacuum filter, and 264.6 g of the separated mother liquor and 19.5 g of crystals were recovered. The obtained crystal was confirmed to be PbSO 4 by X-ray diffraction. The composition of the obtained separated mother liquor and crystals was as shown in Table 3.
〔実施例３〕
３００ｍｌガラス製ビーカーに、水を１１３．７ｇ入れ、更に表１に示す組成のクロム酸鉛廃棄物２２．５ｇと９９．７％無水クロム酸９．１ｇを投入し、充分撹拌してクロム酸含有のクロム酸鉛スラリーを調整した。酸としては試薬の９５％硫酸４０．３ｇを用いた。なお、無水クロム酸の添加は、クロム酸鉛スラリー濃度が約３０％のクロムめっき廃液（クロム酸濃度が２０％）として受け入れることを想定したものである。
Example 3
In a 300 ml glass beaker, 113.7 g of water was added, and then 22.5 g of lead chromate waste and 9.1 g of 99.7% chromic anhydride having the composition shown in Table 1 were added and stirred sufficiently to contain chromic acid. The lead chromate slurry was prepared. As the acid, 40.3 g of 95% sulfuric acid as a reagent was used. The addition of chromic anhydride is assumed to be accepted as a chromium plating waste solution (chromic acid concentration is 20%) having a lead chromate slurry concentration of about 30%.
クロム酸含有のクロム酸鉛スラリーをヒーターで加熱し、液温が４６℃となったところで硫酸を手動で添加した。添加に要した時間は１０分である。添加終了時の液温は６２℃で、この温度で６０分間熟成した。熟成終了後、９ｃｍφのブフナー式真空ろ過器で固液分離し、分離母液１８５．４ｇ並びに結晶１９．２ｇを回収した。得られた結晶はＸ線回折にてＰｂＳＯ4であることが確認された。得られた分離母液と結晶の組成は表４の通りであった。 The chromic acid-containing lead chromate slurry was heated with a heater, and sulfuric acid was manually added when the liquid temperature reached 46 ° C. The time required for the addition is 10 minutes. The liquid temperature at the end of the addition was 62 ° C., and aging was performed at this temperature for 60 minutes. After completion of ripening, solid-liquid separation was performed with a 9 cmφ Buchner vacuum filter, and 185.4 g of the separated mother liquor and 19.2 g of crystals were recovered. The obtained crystal was confirmed to be PbSO 4 by X-ray diffraction. The composition of the obtained separation mother liquor and crystals was as shown in Table 4.
〔実施例４〕
３００ｍｌガラス製ビーカーに、水を１３０．０ｇ入れ、更にクロムめっき業者Ｂから入手した表５に示す組成のクロム酸鉛廃棄物３６．５ｇを投入し、充分撹拌してクロム酸鉛スラリーを調整した。酸としては試薬の９５％硫酸６０．３ｇを用いた。
Example 4
In a 300 ml glass beaker, 130.0 g of water was added, and further 36.5 g of lead chromate waste having the composition shown in Table 5 obtained from the chromium plating supplier B was added and stirred sufficiently to prepare a lead chromate slurry. . As the acid, 60.3 g of 95% sulfuric acid as a reagent was used.
クロム酸鉛スラリーの液温が５５℃で硫酸を手動で滴下して添加した。添加に要した時間は１５分である。必要に応じてヒーターで加熱して液温を６０℃前後に保ちながら６０分間以上熟成した。熟成終了後、９ｃｍφのブフナー式真空ろ過器で固液分離し、分離母液１８８．３ｇ並びに結晶２８．３ｇを回収した。得られた結晶はＸ線回折にてＰｂＳＯ4であることが確認された。得られた分離母液と結晶の組成は表６の通りであった。 The sulfuric acid was manually added dropwise at a liquid temperature of the lead chromate slurry of 55 ° C. The time required for the addition is 15 minutes. The mixture was aged for 60 minutes or more while maintaining the liquid temperature at around 60 ° C. by heating with a heater as necessary. After completion of aging, solid-liquid separation was performed with a 9 cmφ Buchner type vacuum filter, and 188.3 g of separated mother liquor and 28.3 g of crystals were recovered. The obtained crystal was confirmed to be PbSO 4 by X-ray diffraction. The composition of the obtained separated mother liquor and crystals was as shown in Table 6.
〔比較例１〕
３００ｍｌガラス製ビーカーに、水を１４９．０ｇ入れ、更に表１に示す組成のクロム酸鉛廃棄物１５．１ｇと９９．７％無水クロム酸１２．２ｇを投入し、充分撹拌してクロム酸含有のクロム酸鉛スラリーを調整した。酸としては試薬の９５％硫酸３０．１ｇを用いた。なお、無水クロム酸の添加は、クロム酸鉛スラリー濃度が約３０％のクロムめっき廃液（クロム酸濃度が２０％）として受け入れることを想定したものである。
[Comparative Example 1]
Into a 300 ml glass beaker, 149.0 g of water was added, and 15.1 g of lead chromate waste and 12.2 g of 99.7% chromic anhydride having the composition shown in Table 1 were added and stirred sufficiently to contain chromic acid. The lead chromate slurry was prepared. As the acid, 30.1 g of 95% sulfuric acid as a reagent was used. The addition of chromic anhydride is assumed to be accepted as a chromium plating waste solution (chromic acid concentration is 20%) having a lead chromate slurry concentration of about 30%.
室温（１４℃）のクロム酸含有のクロム酸鉛スラリーに硫酸を手動で添加した。添加に要した時間は１０分である。添加終了時の液温は３３℃で、加熱せずに１２０分間熟成した。液温は熟成終了後、室温（１４℃）に戻っており、９ｃｍφのブフナー式真空ろ過器で固液分離し、分離母液２０６．９ｇ並びに結晶１３．７ｇを回収した。得られた結晶はＸ線回折にてＰｂＣｒＯ4が主成分であることが確認された。得られた分離母液と結晶の組成は表７の通りであった。 Sulfuric acid was manually added to a chromic acid-containing lead chromate slurry at room temperature (14 ° C.). The time required for the addition is 10 minutes. The liquid temperature at the end of the addition was 33 ° C., and aging was performed for 120 minutes without heating. The liquid temperature returned to room temperature (14 ° C.) after completion of ripening, and solid-liquid separation was performed with a 9 cmφ Buchner vacuum filter to recover 206.9 g of separated mother liquid and 13.7 g of crystals. The obtained crystal was confirmed by X-ray diffraction to contain PbCrO 4 as a main component. Table 7 shows the composition of the obtained separation mother liquor and crystals.
〔比較例２〕
３００ｍｌガラス製ビーカーに、水を１１３．２ｇ入れ、更に表１に示す組成のクロム酸鉛廃棄物２２．６ｇと９９．７％無水クロム酸９．０ｇを投入し、充分撹拌してクロム酸含有のクロム酸鉛スラリーを調整した。酸としては試薬の９５％硫酸４０．４ｇを用いた。また、反応液の中和には４８．５％苛性ソーダ７１．５ｇを使用した。なお、無水クロム酸の添加は、クロム酸鉛スラリー濃度が約３０％のクロムめっき廃液（クロム酸濃度が２０％）として受け入れることを想定したものである。
[Comparative Example 2]
Into a 300 ml glass beaker, 113.2 g of water was added, and 22.6 g of lead chromate waste having the composition shown in Table 1 and 9.0 g of 99.7% chromic anhydride were added and thoroughly stirred to contain chromic acid. The lead chromate slurry was prepared. As the acid, 40.4 g of 95% sulfuric acid as a reagent was used. Further, 71.5 g of 48.5% caustic soda was used for neutralization of the reaction solution. The addition of chromic anhydride is assumed to be accepted as a chromium plating waste solution (chromic acid concentration is 20%) having a lead chromate slurry concentration of about 30%.
クロム酸含有のクロム酸鉛スラリーをヒーターで加熱し、液温が３７℃になったところで硫酸を手動で添加した。添加に要した時間は１０分である。添加終了時の液温は５７℃で、加熱しながら６０℃前後で６０分間熟成した。熟成終了後、苛性ソーダを添加して中和した。中和に要した時間は２０分である。中和後、９ｃｍφのブフナー式真空ろ過器で固液分離し、分離母液２３６．７ｇ並びに結晶２５．１ｇを回収した。得られた結晶はＸ線回折にてＰｂＣｒＯ4とＰｂＳＯ4の混合物であることが確認された。得られた分離母液と結晶の組成は表８の通りであった。 The chromic acid-containing lead chromate slurry was heated with a heater, and sulfuric acid was manually added when the liquid temperature reached 37 ° C. The time required for the addition is 10 minutes. The liquid temperature at the end of the addition was 57 ° C., and aging was performed at around 60 ° C. for 60 minutes while heating. After completion of aging, caustic soda was added for neutralization. The time required for neutralization is 20 minutes. After neutralization, solid-liquid separation was performed with a 9 cmφ Buchner vacuum filter to recover 236.7 g of the separated mother liquor and 25.1 g of crystals. The obtained crystal was confirmed to be a mixture of PbCrO 4 and PbSO 4 by X-ray diffraction. Table 8 shows the composition of the obtained separation mother liquor and crystals.
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