| 中文名 |
三氯苯
|
| 英文名 |
1,2,4-trichlorobenzene
|
| 中文别名 |
1,2,4-三氯苯
|
| 英文别名 |
1,2,5-Trichlorobenzene
EINECS 204-428-0
1,4,5-trichlorobenzene
1,2,4-Trichlorbenzene
Benzene, 1,2,4-trichloro-
MFCD00000547
1,2,4-trichloro-benzene
Trojchlorobenzen
1,2,4-Trichlorobenzene
Hostetex l-pec
1,2,4-Trichlorbenzol
as-trichlorobenzene
1,2,4-Trichlorobenze
1,2,4-Trichlorobenzol
1,3,4-trichlorobenzene
1,2,4-trichlorobenzene—
Hipochem GM
|
| 密度 |
1.4±0.1 g/cm3
|
| 沸点 |
211.4±20.0 °C at 760 mmHg
|
| 熔点 |
16 °C(lit.)
|
| 分子式 |
C6H3Cl3
|
| 分子量 |
181.447
|
| 闪点 |
126.7±0.0 °C
|
| 精确质量 |
179.930038
|
| LogP |
3.82
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| 外观性状 |
无色液体带有一种令人愉快的气味
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| 蒸汽密度 |
>6 (vs air)
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| 蒸汽压 |
0.3±0.4 mmHg at 25°C
|
| 折射率 |
1.567
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| 储存条件 |
储存注意事项 储存于阴凉、通风的库房。远离火种、热源。保持容器密封。应与氧化剂、食用化学品分开存放,切忌混储。配备相应品种和数量的消防器材。储区应备有泄漏应急处理设备和合适的收容材料。
|
| 稳定性 |
1.干燥纯净的1,2,4-三氯苯对金属无腐蚀性。在热和水作用下,放出微量腐蚀性强的氯化氢。水解生成2,5-二氯苯酚。硝化生成2,4,5-三氯硝基苯。
2.稳定性 稳定
3.禁配物 强氧化剂
4.避免接触的条件 受热
5.聚合危害 不聚合
6.分解产物 氯化氢
|
| 水溶解性 |
INSOLUBLE
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| 分子结构 |
1、摩尔折射率:40.93
2、摩尔体积(cm3/mol):125.2
3、等张比容(90.2K):314.8
4、表面张力(dyne/cm):39.9
5、极化率16.22
|
| 计算化学 |
1.疏水参数计算参考值(XlogP):无
2.氢键供体数量:0
3.氢键受体数量:0
4.可旋转化学键数量:0
5.互变异构体数量:无
6.拓扑分子极性表面积0
7.重原子数量:9
8.表面电荷:0
9.复杂度:94.3
10.同位素原子数量:0
11.确定原子立构中心数量:0
12.不确定原子立构中心数量:0
13.确定化学键立构中心数量:0
14.不确定化学键立构中心数量:0
15.共价键单元数量:1
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| 更多 |
1.性状:无色液体
2.熔点(℃):17
3.沸点(℃):213.5
4.相对密度(水=1):1.45
5.相对蒸气密度(空气=1):6.26
6.饱和蒸气压(kPa):0.13(38.4℃)
7.燃烧热(kJ/mol):-2798.7
8.临界压力(MPa):3.72
9.辛醇/水分配系数:4.02
10.闪点(℃):105(CC)
11.引燃温度(℃):571
12.爆炸上限(%):6.6
13.爆炸下限(%):2.5
14.溶解性:不溶于水,微溶于醇,可混溶于乙醚、苯、石油醚、二硫化碳及多数有机溶剂。
15.黏度(mPa·s,55.4ºC):1.5732
16.蒸发热(KJ/mol):15.5
17.熔化热(KJ/mol):62.4
18.常温折射率(n20):1.5717
19.常温折射率(n25):1.5693
20.溶度参数(J·cm-3)0.5:20.618
21.van der Waals面积(cm2·mol-1):1.233×1010
22.van der Waals体积(cm3·mol-1):100.980
23.液相标准热熔(J·mol-1·K-1):202.5
24.气相标准声称热(焓)( kJ·mol-1) :22.5
25.气相标准热熔(J·mol-1·K-1):129.13
|
毒理学数据:
1、急性毒性:
大鼠经口LD50:756mg/kg;大鼠经皮下LD50:6139mg/kg;小鼠经口LD50:300mg/kg;小鼠腹膜腔LD50:1223mg/kg;
2、其它多剂量毒性:大鼠经口TDLO:280mg/kg/14D-C;大鼠经口TDLO:7380mg/kg/13W-C;
3、生殖数据:大鼠经口TDLO:1800mg/kg/25W-I;大鼠(雌)腹膜腔TDLO:750mg/kg/3D;
4、致突变毒性:小鼠微核试验:210mg/kg/24H;5、毒性和二氯苯相同,对上呼吸道及黏膜刺激。嗅觉阈浓度0.01mg/L(水质)。
5.急性毒性
LD50:756mg/kg(大鼠经口);6139mg/kg(大鼠经皮);6100mg/kg(兔经皮)
6.刺激性 家兔经皮:1950mg(13周,间断),中度刺激。
7.致突变性 微核试验:小鼠腹腔内给予最低中毒剂量(TDLo)210mg/kg(24h)
生态学数据:
1.生态毒性 LC50:1.95mg/L(48h)(虹鳟鱼);109mg/L(24h),13mg/L(48h),3.36mg/L(96h)(蓝鳃太阳鱼);2.92mg/L(96h)(黑头呆鱼)
2.生物降解性
好氧生物降解(h):672~4320
厌氧生物降解(h):2688~17280
3.非生物降解性
光解最大光吸收波长范围(nm):278~286
空气中光氧化半衰期(h):128.4~1284
一级水解半衰期(h):29784
4.生物富集性 BCF:420~1140(鲤鱼,接触浓度50μg/L,接触时间6周);120~1300(鲤鱼,接触浓度5μg/L,接触时间6周)
CHEMICAL IDENTIFICATION
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RTECS NUMBER :
-
DC2100000
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CHEMICAL NAME :
-
Benzene, 1,2,4-trichloro-
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CAS REGISTRY NUMBER :
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120-82-1
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BEILSTEIN REFERENCE NO. :
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0956819
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LAST UPDATED :
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199712
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DATA ITEMS CITED :
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31
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MOLECULAR FORMULA :
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C6-H3-Cl3
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MOLECULAR WEIGHT :
-
181.44
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WISWESSER LINE NOTATION :
-
GR BG DG
HEALTH HAZARD DATA
ACUTE TOXICITY DATA
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TYPE OF TEST :
-
Standard Draize test
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ROUTE OF EXPOSURE :
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Administration onto the skin
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SPECIES OBSERVED :
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Rodent - rabbit
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TYPE OF TEST :
-
LD50 - Lethal dose, 50 percent kill
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ROUTE OF EXPOSURE :
-
Oral
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SPECIES OBSERVED :
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Rodent - rat
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DOSE/DURATION :
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756 mg/kg
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TOXIC EFFECTS :
-
Behavioral - somnolence (general depressed activity) Behavioral - convulsions or effect on seizure threshold
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TYPE OF TEST :
-
LD50 - Lethal dose, 50 percent kill
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ROUTE OF EXPOSURE :
-
Administration onto the skin
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SPECIES OBSERVED :
-
Rodent - rat
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DOSE/DURATION :
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6139 mg/kg
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TOXIC EFFECTS :
-
Behavioral - somnolence (general depressed activity) Behavioral - convulsions or effect on seizure threshold
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TYPE OF TEST :
-
LD50 - Lethal dose, 50 percent kill
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ROUTE OF EXPOSURE :
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Oral
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SPECIES OBSERVED :
-
Rodent - mouse
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DOSE/DURATION :
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300 mg/kg
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TOXIC EFFECTS :
-
Behavioral - altered sleep time (including change in righting reflex) Behavioral - convulsions or effect on seizure threshold Behavioral - ataxia
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TYPE OF TEST :
-
LD50 - Lethal dose, 50 percent kill
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ROUTE OF EXPOSURE :
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Intraperitoneal
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SPECIES OBSERVED :
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Rodent - mouse
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DOSE/DURATION :
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1223 mg/kg
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TOXIC EFFECTS :
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Details of toxic effects not reported other than lethal dose value
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TYPE OF TEST :
-
TDLo - Lowest published toxic dose
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ROUTE OF EXPOSURE :
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Oral
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SPECIES OBSERVED :
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Rodent - rat
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DOSE/DURATION :
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280 mg/kg/14D-C
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TOXIC EFFECTS :
-
Biochemical - Enzyme inhibition, induction, or change in blood or tissue levels - other oxidoreductases
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TYPE OF TEST :
-
TDLo - Lowest published toxic dose
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ROUTE OF EXPOSURE :
-
Oral
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SPECIES OBSERVED :
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Rodent - rat
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DOSE/DURATION :
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7380 mg/kg/13W-C
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TOXIC EFFECTS :
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Liver - changes in liver weight Kidney, Ureter, Bladder - changes in bladder weight Biochemical - Enzyme inhibition, induction, or change in blood or tissue levels - hepatic microsomal mixed oxidase (dealkylation, hydroxylation, etc.)
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TYPE OF TEST :
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TDLo - Lowest published toxic dose
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ROUTE OF EXPOSURE :
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Oral
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DOSE :
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1800 mg/kg
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SEX/DURATION :
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female 9-13 day(s) after conception
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TOXIC EFFECTS :
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Reproductive - Effects on Embryo or Fetus - cytological changes (including somatic cell genetic material) Reproductive - Effects on Embryo or Fetus - fetotoxicity (except death, e.g., stunted fetus) Reproductive - Effects on Embryo or Fetus - fetal death
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TYPE OF TEST :
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TDLo - Lowest published toxic dose
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ROUTE OF EXPOSURE :
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Intraperitoneal
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DOSE :
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750 mg/kg
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SEX/DURATION :
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female 3 day(s) pre-mating
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TOXIC EFFECTS :
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Reproductive - Maternal Effects - uterus, cervix, vagina
MUTATION DATA
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TEST SYSTEM :
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Rodent - mouse
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REFERENCE :
-
MUTAEX Mutagenesis. (Oxford Univ. Press, Pinkhill House, Southfield Road, Eynsham, Oxford OX8 1JJ, UK) V.1- 1986- Volume(issue)/page/year: 2,111,1987 *** REVIEWS *** ACGIH TLV-CL 37 mg/m3 (5 ppm) DTLVS* The Threshold Limit Values (TLVs) and Biological Exposure Indices (BEIs) booklet issues by American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH, 1996 Volume(issue)/page/year: TLV/BEI,1997 *** OCCUPATIONAL EXPOSURE LIMITS *** OEL-AUSTRALIA:TWA 5 ppm (40 mg/m3) JAN 1993 OEL-BELGIUM:STEL 5 ppm (37 mg/m3) JAN 1993 OEL-DENMARK:TWA 5 ppm (40 mg/m3) JAN 1993 OEL-FINLAND:TWA 5 ppm (40 mg/m3);STEL 10 ppm (74 mg/m3);Skin JAN 1993 OEL-FRANCE:TWA 5 ppm (40 mg/m3) JAN 1993 OEL-GERMANY:TWA 5 ppm (40 mg/m3) JAN 1993 OEL-THE NETHERLANDS:TWA 5 ppm (40 mg/m3) JAN 1993 OEL-SWITZERLAND:TWA 5 ppm (40 mg/m3) JAN 1993 OEL-UNITED KINGDOM:TWA 5 ppm (40 mg/m3);STEL 5 ppm (40 mg/m3) JAN 1993 OEL IN BULGARIA, COLOMBIA, JORDAN, KOREA check ACGIH TLV OEL IN NEW ZEALAND, SINGAPORE, VIETNAM check ACGIH TLV *** NIOSH STANDARDS DEVELOPMENT AND SURVEILLANCE DATA *** NIOSH RECOMMENDED EXPOSURE LEVEL (REL) : NIOSH REL TO 1,2,4-TRICHLOROBENZENE-air:CL 5 ppm REFERENCE : NIOSH* National Institute for Occupational Safety and Health, U.S. Dept. of Health, Education, and Welfare, Reports and Memoranda. Volume(issue)/page/year: DHHS #92-100,1992 NIOSH OCCUPATIONAL EXPOSURE SURVEY DATA : NOHS - National Occupational Hazard Survey (1974) NOHS Hazard Code - 83334 No. of Facilities: 74 (estimated) No. of Industries: 4 No. of Occupations: 8 No. of Employees: 1687 (estimated) NOES - National Occupational Exposure Survey (1983) NOES Hazard Code - 83334 No. of Facilities: 78 (estimated) No. of Industries: 6 No. of Occupations: 14 No. of Employees: 4033 (estimated) No. of Female Employees: 1463 (estimated)
|
【方法一】
1,2,4-三氯苯的制备以六六六无毒异构体为原料,可采用热分解、碱水分解、石灰乳分解三种方法制得,所得产品中含有少量1,2,3-三氯苯和1,3,5-三氯苯。
此法得到的1,2,4-三氯苯含量最高。
工艺过程为六六六无毒异构体与消石灰(50%~60%)的质量比为1∶0.666,水的用量为消石灰的10倍以上。操作时先取400kg六六六无毒异构体加入脱氯化氢器内,再将消石灰230kg、水3t-同加入配料槽内,搅拌20min后,再用泵送入脱氯化氢器内。通入蒸汽预热至60℃时开始往冷凝器夹层内放入冷水,至90℃时停止直接蒸汽加热,瞬间器内即沸腾。控制蒸汽压力为53.2~66.5kPa,调节冷凝水,使出口水温在50~55℃。三氯苯随水蒸气蒸出,经冷凝器冷凝而进入分液器内。因三氯苯比水重,所以沉于器底。由水上部溢流管流回脱氯化氢器内再利用。反应时间共8h,三氯苯即全部蒸出。然后停止加热,由分液器底部将三氯苯放人大桶即为成品;未反应的残渣由脱氯化氢器下口排入下水道。此法中熔化石灰石需1.3h,脱氯化氢需9.6h,共计约需11h。
另一工艺过程为:水解温度210~215℃,压力1.96MPa,石灰乳过量10%条件下,将甲乙体完全分解为三氯苯,因此产率高,可达94%以上,无明显副反应,避免热解碳化物引起职业病,产品质量高,含1,2,4-三氯苯90%以上,排出废渣少,废液不多,易于综合利用,设备简单,生产强度高,但成本高于热解法,且水解釜腐蚀严重。
烧碱加压水解法
以六六六无毒体为原料,经与烧碱液混合,在加压下水解而得。
此法水解温度180℃,压力0.98MPa,用联苯醚锅炉加热,反应70~80min后得到三氯苯,收率约94%。水解釜腐蚀速度较慢,为高压石灰乳法的11%,可消除职业中毒,解决了环境污染问题。此法流程短,生产稳定,操作方便,工艺可行,但消耗碱,成本高,比石灰乳法产品中1,2,4-三氯苯含量低。
(3)热解法
此法工艺过程简单,设备生产强度大,能回收副产盐酸,成本低,但职业中毒严重。
过去1,2,4-三氯苯主要依靠林丹副产的无效体加工成混合三氯苯,再分馏而得1,2,4-三氯苯。随着对林丹的限制,传统的三氯苯原料日益减少,国外目前工业化方法为二氯苯选择性氯化得到三氯苯混合物,然后采用分子筛吸附解析法和分子筛选择性异构化法先进技术,分离得到高纯度的1,2,4-三氯苯。
【方法二】
1.热解法干燥的六六六无毒体在热解釜中加热热即得三氯苯,同时副产大量氯化氢。2.碱解法六六六无毒体与石灰乳共热即得三氯苯,同时副产大量氯化钙液。上述二法所得三氯苯均为1,2,4-三氯苯;1,3,5-三氯苯;1,2,3-三氯苯三种异构体的混合物,以1,2,4-三氯苯为主要组分。石灰乳法生产的三氯苯中,1,2,4-三氯苯含量在75%以上,1,2,3-三氯苯约占20%。
| 海关编码 |
2903999090
|
| 中文概述 |
2903999090 其他芳烃卤化衍生物. 增值税率:17.0% 退税率:9.0% 监管条件:无 最惠国关税:5.5% 普通关税:30.0%
|
| 申报要素 |
品名, 成分含量, 用途
|
| Summary |
2903999090 halogenated derivatives of aromatic hydrocarbons VAT:17.0% Tax rebate rate:9.0% Supervision conditions:none MFN tariff:5.5% General tariff:30.0%
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