CN1009072B - 破坏副产物四硝基甲烷的工艺 - Google Patents
破坏副产物四硝基甲烷的工艺Info
- Publication number
- CN1009072B CN1009072B CN87102764A CN87102764A CN1009072B CN 1009072 B CN1009072 B CN 1009072B CN 87102764 A CN87102764 A CN 87102764A CN 87102764 A CN87102764 A CN 87102764A CN 1009072 B CN1009072 B CN 1009072B
- Authority
- CN
- China
- Prior art keywords
- tnm
- nitric acid
- tetranitromethane
- product
- technology
- 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.)
- Expired
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/02—Formation or introduction of functional groups containing nitrogen of nitro or nitroso groups
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/06—Explosives, propellants or pyrotechnics, e.g. rocket fuel or napalm
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S149/00—Explosive and thermic compositions or charges
- Y10S149/124—Methods for reclaiming or disposing of one or more materials in a composition
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Emergency Management (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Control Of El Displays (AREA)
- Gyroscopes (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Treating Waste Gases (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyridine Compounds (AREA)
Abstract
一种处理副产物四硝基甲烷(TNM)的工艺，该工艺避免了现有技术在分离和提取步骤中的危险。将一种从硝化或硝酸氧化工厂得来的含有TNM的厂内选择液体或蒸汽流或反应器废气流加热，有效地裂解TNM，而不会过份损失硝酸值。
Description
本发明涉及用硝酸处理有机物的方法。特别是本发明提供一个分离的二级处理方法用于先期阻止和经济连续地破坏基于硝酸的氧化或硝化反应中的危险副产物。
所述的硝化及氧化反应是众所周知并广泛地用于工业上。由它们提供有价值的产品，如炸药和制造药物的中间体、染料、塑料、杀虫剂和其他许多工业上的有用物质。但鲜为人知的是很多这种方法亦都产生一定量的危险副产物-四硝基甲烷（TNM）。
TNM的危险有两个原因。首先是它的高度毒性，它能很快地通过皮肤接触和蒸汽吸入被吸收。其次，虽然TNM在纯状态下不是一种炸药，但它很容易溶解烃类和其它非极性燃料，产生一种水不相溶稠密的爆炸性液体，它具有很大的爆炸力和高度的敏感性。
其他工艺过程所产生的TNM副产物的量一般十分少，然而，当今在回收和再浓缩含氮烟雾和废硝酸中残余硝酸的实际操作中，造成TNM再循环到回收硝酸的反应器。即使产生的TNM量很少，但是由于不断的积累使TNM的浓度增加，因而增加了存在的潜在危险。
TNM杂质存在在产品中所引起的危险是已知的。三硝基甲苯的毒性对弹药库工作人员来说是很明显的。一些硝化甘油基的炸药已显示出安全储存时间的减少。为了避免这些问题，产品用弱碱性的亚硫酸盐溶液来洗涤，经处理后，TNM作为有毒的三硝基甲烷被萃取到洗液中，而这种处理对水溶性产品是不可能的。
TNM是挥发性物质，常常部分的TNM从其生成的反应器中以蒸汽的
形式从反应器排出气体中逸出。这些气体另外含有氧化氮并且通常是硝酸蒸汽，为了分离这些气体物质和防止环境污染，设计的回收步骤包括用稀硝酸洗涤这种经空气稀释的气体。TNM不会受此步骤的影响，将会通过此系统和烟道气一同排出。这会引起污染的危害和TNM中可回收氮量的浪费。亦有可能TNM在冷的条件下被冷凝成为一个分离的液相存在于吸收体中，这具有明显的潜在危险。已经研制出一些方法，用来尽量减少这些排放物和从任何这类烟道气中吸收TNM作为可销售衍生物。美国专利4001373和4003977号介绍了用碱性水溶液洗涤气流吸收三硝基甲基盐形式的TNM。接着酸化废洗涤液并放出三硝基甲烷。这也是和TNM性质十分相似，具有潜在危险的物质。上述方法的缺点包括，当处理气体中二氧化碳的含量较高时碱的用量就很大。由于这原因及所需设备的寸尺和复杂性阻碍了此方法的广泛应用。
当化学反应器在中温或低温下运作时，副产物TNM会留在废酸溶液中。回收操作倾向于在高浓度的硝酸中浓缩挥发性和亲油性的TNM，并循环此物质。美国专利3781374号介绍了从一种硝酸源分离TNM的方法。小心蒸馏硝酸得到一种极易挥发馏份，使得在浓度超过99%的硝酸中TNM的共沸浓度达到30%。分离此馏份，用水稀释和冷却，在稀硝酸下层得到TNM分离层。放出TNM，并连续用水洗涤得到可用于销售质量的TNM。同时产生的稀硝酸流以较高的费用来浓缩和循环。在方法上的经济问题，TNM需求量低和处理该纯物质时的危险性妨碍了此发明的广泛应用。
因此需要一种能够完全避免由于作为副产物存在的TNM所引起的毒性和爆炸危险的简单方法。
因此本发明的目的是提供一种安全和经济的方法来破坏基于硝酸的方法中的副产物。亦即避免了已知方法中存在的危险和缺点。
本发明的另一目的是提供一种破坏而又不损失有价值可回收氮组份的方法。这些氮组份包括破坏过程中自然形成的氮氧化物。另外少量的
氧化物是由于硝酸的自然分解而生成的。
特别是本发明的方法即使在有其他气体包括硝酸蒸汽存在下，也可选择性地破坏TNM，包括将含有TNM的混合物加热到215°至300℃，较好是220°至300℃，最好是220°至250℃，于此温度下保持0.1至200秒，较好是0.5至100秒，最好保持0.5至5秒，接着冷却产生的混合物，并通过其他步骤回收存在的有价值的氮组份。
TNM在高温下分解早为人们所熟悉，然而意外地发现较经济地对TNM进行先期阻止时所必需的本身性质不稳定的硝酸，在经受到足以破坏TNM的剧烈热处理后，大部分可以完好地保留下来。本发明在经济上的成功很大程度归功于此意外的发现。因为即使用氧化氮来补充硝酸的浓度在技术上是可行的，但费用昂贵。这是由于此方法需用庞大的设备来吸收稀硝酸，并且在紧接着的浓缩过程中需要大量的能量。
为了能更易了解本发明，通过下面实例来说明最佳的实施方案。
例Ⅰ
一个使用硝酸作为硝化介质，用于硝化芳香化合物来生产塑料中间体的方法。从硝化反应器排出的产物混合物是一种塑料中间体的硝酸溶液，然后送入降膜蒸发器中，大部分硝酸和TNM在蒸发器的顶部作为蒸汽被除去。该蒸汽经二级冷凝得到2250公斤/小时浓度高于99%的硝酸，其中含13.5公斤/小时TNM[包括溶解的氮氧化物（NOX）]。这是一种更易挥发的冷凝液。经一漂白器汽提出大部分溶解的NOX以后，将汽提过的冷凝物送进一个连续蒸馏塔。一个挥发性最大的塔顶馏份（44公斤/小时浓度高于99%的硝酸其中含12公斤/小时TNM）作为气体和一些残留的NOX和氧一道排出。在没有冷凝的情况下把此气体和蒸汽流，送进一个由钽管组成的热解器中。管子通过外部电器元件加热使气体混合物经过该管时，其温度达到250℃，而管的体积要做成使气体停留时间为一秒。在此单元中99%的TNM转化成氧化碳和氮的氧化物，而被分解的
硝酸则少于40%。所有这些混合气体产物与稀释空气一同被送进一废气洗涤塔，在其中硝酸和NOX（来自硝化装置的不同部分）被稀硝酸吸收。从塔中得到的强化稀硝酸可通过再浓缩来回收，而由分解TNM产生的碳氧化物则排放到大气中。
例Ⅱ
一种耐化学性氯化芳香基质的硝化系统，该系统生产一种除草剂中间体，在一组串连的反应器中，在100°-115°下使用一个浓硝酸和硫酸的混合物。反应器组的排出气体是60公斤/小时的混合物，其中以重量计氯和氯化氢占11%;二氧化碳占55%;一氧化碳占1%;硝酸蒸汽占25%;TNM占4.5%。将此气体混合物通进由电热石英管组成的热解装置，将气体混合物的温度升至250℃保持一秒钟。此热解破坏了99%以上的TNM，而99%的硝酸未被分解。将此气体流通进一个冷凝器，然后通到一个以硫酸为吸收液的气体洗涤器中，从而有效地除去所有的硝酸和NOX，剩下氯，氯化氢和二氧化碳，接着经选择吸收装置处理后，再排放到大气中。在硫酸中的硝酸和NOX接着用来生产新的硝化酸混合物。
对本技术领域的专业人员很明显TNM的热解是在几个连接部分进行的，但最好是在TNM浓度最高的部分实施本发明，这样加热和冷却的设备会最少。最好亦尽量减少硝酸同时加到热解环境中的量，这样会尽量减少酸的分解和再生费用的损失。通常最好将热解安排在先，然后再将蒸汽或气体流送进一个吸收装置。
Claims (8)
1、在用硝酸处理有机物质而产生作为副产物四硝基甲烷的化学方法中，其改进包括使含有四硝基甲烷的部分经受至少210℃的温度，从而将四硝基甲烷分解。
2、根据权利要求1所述的方法，其中将所述含四硝基甲烷的部分加热到210°至300℃，时间为0.1至200秒。
3、根据权利要求1所述的方法，其中硝酸处理过程是一个硝化过程。
4、根据权利要求1所述的方法，其中硝酸处理过程是一个氧化过程。
5、根据权利要求1所述的方法，其中所述含四硝基甲烷的部分包括废气和蒸汽。
6、根据权利要求5所述的方法，其中所述废气和蒸汽加热到220°至250℃，时间为0.5至100秒。
7、根据权利要求1所述的方法，其中所述含四硝基甲烷的部分包括浓度高于99%的硝酸。
8、根据权利要求7所述的方法，其中所述硝酸加热到温度220°至250℃，时间为0.5至100秒。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA506,238 | 1986-04-09 | ||
| CA000506238A CA1242459A (en) | 1986-04-09 | 1986-04-09 | Process for the destruction of by-product tetranitromethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87102764A CN87102764A (zh) | 1987-11-18 |
| CN1009072B true CN1009072B (zh) | 1990-08-08 |
Family
ID=4132845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87102764A Expired CN1009072B (zh) | 1986-04-09 | 1987-04-09 | 破坏副产物四硝基甲烷的工艺 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4713232A (zh) |
| EP (1) | EP0241194B1 (zh) |
| JP (1) | JPS62244425A (zh) |
| KR (1) | KR890003833B1 (zh) |
| CN (1) | CN1009072B (zh) |
| AT (1) | ATE45886T1 (zh) |
| AU (1) | AU583452B2 (zh) |
| CA (1) | CA1242459A (zh) |
| DE (1) | DE3760490D1 (zh) |
| ES (1) | ES2011048B3 (zh) |
| FI (1) | FI871354A (zh) |
| NO (1) | NO871473L (zh) |
| NZ (1) | NZ219625A (zh) |
| PT (1) | PT84636B (zh) |
| ZA (1) | ZA872182B (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3813184A1 (de) * | 1988-04-20 | 1989-11-02 | Dynamit Nobel Ag | Verfahren zur zersetzung von in abwaessern geloesten explosionsfaehigen salpetersaeureestern |
| US5589037A (en) * | 1995-10-24 | 1996-12-31 | General Electric Company | Method for removing tetranitromethane from nitric acid |
| AU2724197A (en) * | 1996-04-16 | 1997-11-07 | Arco Chemical Technology L.P. | Reducing tetranitromethane in compositions containing nitroaromatic compounds |
| US5847240A (en) * | 1997-03-24 | 1998-12-08 | Arco Chemical Technology, L.P. | Process for reducing tetranitromethane in compositions containing nitroaromatic compounds |
| US6414143B1 (en) | 1999-02-24 | 2002-07-02 | Alliant Techsystems Inc. | Extraction and recovery of nitramines from propellants, explosives, and pyrotechnics |
| US6610156B2 (en) * | 2000-03-10 | 2003-08-26 | Alliant Techsystems Inc. | Method for recovery of nitramines from aluminized energetic materials |
| US6416601B1 (en) | 2000-03-10 | 2002-07-09 | Alliant Techsystems Inc. | Method of recovery for nitramines from aluminized energetic materials |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1632959A (en) * | 1923-12-31 | 1927-06-21 | Gartner Richard Hans | Method for removing tetranitromethane from trinitrotoluene |
| US2366309A (en) * | 1941-04-17 | 1945-01-02 | Du Pont | Apparatus for the treatment of waste acid |
| US3781374A (en) * | 1972-08-03 | 1973-12-25 | Nitro Nobel Ab | Method for the isolation of tetranitromethane from a solution of nitric acid with comparatively low contents of tetranitromethane |
| US4001373A (en) * | 1975-08-18 | 1977-01-04 | The United States Of America As Represented By The Secretary Of The Navy | Removal of tetranitromethane from tnt plant waste |
| US4003977A (en) * | 1975-08-18 | 1977-01-18 | The United States Of America As Represented By The Secretary Of The Navy | Removal of tetranitromethane from TNT plant waste gases |
-
1986
- 1986-04-09 CA CA000506238A patent/CA1242459A/en not_active Expired
- 1986-08-13 US US06/896,094 patent/US4713232A/en not_active Expired - Fee Related
-
1987
- 1987-03-16 NZ NZ219625A patent/NZ219625A/xx unknown
- 1987-03-17 AU AU70097/87A patent/AU583452B2/en not_active Ceased
- 1987-03-25 ZA ZA872182A patent/ZA872182B/xx unknown
- 1987-03-27 FI FI871354A patent/FI871354A/fi not_active IP Right Cessation
- 1987-03-30 AT AT87302722T patent/ATE45886T1/de active
- 1987-03-30 EP EP87302722A patent/EP0241194B1/en not_active Expired
- 1987-03-30 ES ES87302722T patent/ES2011048B3/es not_active Expired
- 1987-03-30 DE DE8787302722T patent/DE3760490D1/de not_active Expired
- 1987-04-06 JP JP62083134A patent/JPS62244425A/ja active Pending
- 1987-04-08 NO NO871473A patent/NO871473L/no unknown
- 1987-04-08 PT PT84636A patent/PT84636B/pt unknown
- 1987-04-08 KR KR1019870003351A patent/KR890003833B1/ko active IP Right Grant
- 1987-04-09 CN CN87102764A patent/CN1009072B/zh not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES2011048B3 (es) | 1989-12-16 |
| CA1242459A (en) | 1988-09-27 |
| KR890003833B1 (ko) | 1989-10-05 |
| EP0241194B1 (en) | 1989-08-30 |
| AU583452B2 (en) | 1989-04-27 |
| PT84636A (en) | 1987-05-01 |
| NO871473D0 (no) | 1987-04-08 |
| EP0241194A1 (en) | 1987-10-14 |
| ATE45886T1 (de) | 1989-09-15 |
| AU7009787A (en) | 1987-10-15 |
| CN87102764A (zh) | 1987-11-18 |
| JPS62244425A (ja) | 1987-10-24 |
| NO871473L (no) | 1987-10-12 |
| US4713232A (en) | 1987-12-15 |
| PT84636B (en) | 1989-05-12 |
| ZA872182B (en) | 1987-11-25 |
| FI871354A (fi) | 1987-10-10 |
| KR870009976A (ko) | 1987-11-30 |
| FI871354A0 (fi) | 1987-03-27 |
| DE3760490D1 (en) | 1989-10-05 |
| NZ219625A (en) | 1989-03-29 |
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