CN100387559C - Method for producing limonene from waste rubber tires - Google Patents
Method for producing limonene from waste rubber tires Download PDFInfo
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- CN100387559C CN100387559C CNB2006100506574A CN200610050657A CN100387559C CN 100387559 C CN100387559 C CN 100387559C CN B2006100506574 A CNB2006100506574 A CN B2006100506574A CN 200610050657 A CN200610050657 A CN 200610050657A CN 100387559 C CN100387559 C CN 100387559C
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- Prior art keywords
- limonene
- waste rubber
- rubber tires
- producing
- supercritical
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- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229940087305 limonene Drugs 0.000 title claims abstract description 56
- 235000001510 limonene Nutrition 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 239000010920 waste tyre Substances 0.000 claims description 11
- 238000012691 depolymerization reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
(一)技术领域(1) Technical field
本发明涉及废橡胶轮胎的再利用回收，特别涉及利用废橡胶轮胎生产柠檬烯的方法。The invention relates to the recycling of waste rubber tires, in particular to a method for producing limonene from waste rubber tires.
(二)背景技术(2) Background technology
随着社会经济的快速发展，我国汽车的保有量快速增加，越来越多的废旧轮胎形成的″黑色污染″正在威胁着全人类的生存环境。据统计，全世界每年约有10亿只轮胎报废，其中能够得到翻新利用的只占15％～20％。为此，许多国家都在千方百计为废旧轮胎寻找出路。中国是世界轮胎生产大国，废旧轮胎的生成量急剧增加，″黑色污染″造成的危害会远远大于″白色污染″。因此，国家环保总局已经将废旧轮胎的回收处理列入21世纪议程。目前，世界上废旧轮胎的处理方式大致有以下几种：一种是用于生产胶粉，一种是作为燃料，特别是发电厂和造纸厂的辅助燃料，还有是热解为油、气和固态炭黑等可回收利用的物质，其中将其热解多是含苯、甲苯、二甲苯以及柠檬烯等成分，但柠檬烯含量低，无工业应用价值。With the rapid development of social economy, the number of automobiles in my country has increased rapidly, and the "black pollution" formed by more and more waste tires is threatening the living environment of all human beings. According to statistics, about 1 billion tires are scrapped every year in the world, of which only 15% to 20% can be refurbished. For this reason, many countries are doing everything possible to find a way out for waste tires. China is the world's largest producer of tires, and the amount of waste tires is increasing sharply. The harm caused by "black pollution" will be far greater than that of "white pollution". Therefore, the State Environmental Protection Administration has included the recycling of waste tires in the 21st century agenda. At present, the disposal methods of waste tires in the world are roughly as follows: one is used to produce rubber powder, the other is used as fuel, especially as auxiliary fuel for power plants and paper mills, and the other is pyrolyzed into oil and gas. Recyclable substances such as carbon black and solid carbon black, among which most of them contain benzene, toluene, xylene and limonene when they are pyrolyzed, but the limonene content is low and has no industrial application value.
(三)发明内容(3) Contents of the invention
本发明的目的是提供一种利用废橡胶轮胎生产柠檬烯的方法，工艺简单，成本低廉，适合规模化生产。The object of the present invention is to provide a method for producing limonene by using waste rubber tires, which has simple process, low cost and is suitable for large-scale production.
本发明采用的技术方案如下：The technical scheme that the present invention adopts is as follows:
一种利用废橡胶轮胎生产柠檬烯的方法，步骤如下：A method utilizing waste rubber tires to produce limonene, the steps are as follows:
(1)将废橡胶轮胎在超临界甲苯中进行解聚，所述的解聚反应是在压力为3.7～4.6MPa，温度为315～370℃条件下反应20～90min，得柠檬烯混合物；(1) Depolymerize waste rubber tires in supercritical toluene, the depolymerization reaction is to react at a pressure of 3.7 to 4.6 MPa and a temperature of 315 to 370°C for 20 to 90 minutes to obtain a limonene mixture;
(2)将超临界解聚得到的混合物进行蒸馏，收集170～180℃的馏分，得到柠檬烯粗品，其它组分可以作为燃料。(2) Distill the mixture obtained by supercritical depolymerization, collect fractions at 170-180° C. to obtain crude limonene, and other components can be used as fuel.
(3)将柠檬烯粗品进行精馏，收集175～177℃的馏分，得柠檬烯产品。(3) Carry out rectification of the crude limonene product, collect the distillate at 175-177° C., and obtain the limonene product.
在所述的利用废橡胶轮胎生产柠檬烯的方法中，所述的超临界甲苯与废轮胎的用量比为5～10∶1，所述的解聚的反应温度推荐控制在325～340℃，更优推荐330℃，所述的解聚反应优选时间为40min～50min，所述的解聚反应压力推荐为4.4～4.6Mpa。In the method for producing limonene from waste rubber tires, the ratio of the amount of supercritical toluene to waste tires is 5-10:1, and the reaction temperature of the depolymerization is recommended to be controlled at 325-340°C, preferably The preferred temperature is 330°C, the preferred time for the depolymerization reaction is 40min-50min, and the recommended pressure for the depolymerization reaction is 4.4-4.6Mpa.
进一步，所述的甲苯与废轮胎的质量比为8∶1。Further, the mass ratio of toluene to waste tires is 8:1.
具体的，所述的利用废橡胶轮胎生产柠檬烯的方法是：Specifically, the described method of utilizing waste rubber tires to produce limonene is:
(1)将废橡胶轮胎置于质量为其8倍的超临界甲苯中进行解聚，所述的解聚反应是在压力为4.5MPa，温度为330℃条件下反应40min，得柠檬烯混合物；(1) Depolymerize waste rubber tires in supercritical toluene whose mass is 8 times its mass, and the depolymerization reaction is to react at a pressure of 4.5 MPa and a temperature of 330° C. for 40 minutes to obtain a limonene mixture;
(2)将超临界解聚得到的混合物进行蒸馏，收集170～180℃的馏分，得到柠檬烯粗品。(2) Distilling the mixture obtained by supercritical depolymerization, collecting fractions at 170-180° C. to obtain crude limonene.
(3)将柠檬烯粗品进行精馏，收集175～177℃的馏分，得柠檬烯产品。(3) Carry out rectification of the crude limonene product, collect the distillate at 175-177° C., and obtain the limonene product.
本发明利用废轮胎生产柠檬烯的方法与现有生产工艺相比，利用了超临界流体甲苯，降低了生产成本，同时也简化了生产工艺。100份重量的废轮胎可生产5～8份的柠檬烯，它可大大减少废旧轮胎对环境造成的污染，实现废物利用。Compared with the existing production process, the method for producing limonene by using waste tires in the present invention utilizes supercritical fluid toluene, reduces production cost, and simplifies the production process at the same time. 100 parts by weight of waste tires can produce 5-8 parts of limonene, which can greatly reduce the environmental pollution caused by waste tires and realize waste utilization.
(四)具体实施方式：(4) Specific implementation methods:
以下以具体实施例来说明本发明的技术方案，但本发明的保护范围不限于此：The technical scheme of the present invention is described below with specific examples, but protection scope of the present invention is not limited thereto:
实施例1Example 1
1、将25g废橡胶轮胎和200g甲苯加入高压釜中加热到330℃，4.4MPa下并恒温恒压40min，得到210.8g柠檬烯混合物。1. Add 25g of waste rubber tires and 200g of toluene into an autoclave and heat to 330°C, 4.4MPa and constant temperature and pressure for 40min to obtain 210.8g of limonene mixture.
2、将超临界解聚得到的混合物进行蒸馏，收集170～180℃的馏分，得到5.4g柠檬烯粗品。2. Distill the mixture obtained by supercritical depolymerization, collect fractions at 170-180° C., and obtain 5.4 g of crude limonene.
3、再将柠檬烯粗品进行精馏，收集175～177℃的馏分，得1.7g柠檬烯产品。3. Carry out rectification on the crude limonene product, collect the fraction at 175-177°C, and obtain 1.7g of limonene product.
实施例2Example 2
1、将20g废橡胶轮胎和200g甲苯加入高压釜中加热到335℃，4.2MPa压力下恒温恒压反应40min，得到206.4g柠檬烯混合物。1. Add 20g of waste rubber tires and 200g of toluene into an autoclave and heat to 335°C, and react under constant temperature and pressure for 40min under a pressure of 4.2MPa to obtain 206.4g of limonene mixture.
2、将超临界解聚得到的混合物进行蒸馏，收集170～180℃的馏分，得到4.3g柠檬烯粗品。2. Distill the mixture obtained by supercritical depolymerization, collect fractions at 170-180° C., and obtain 4.3 g of crude limonene.
3、再将柠檬烯粗品进行精馏，收集175～177℃的馏分，得1.2g柠檬烯产品。3. Rectify the crude limonene, collect the fraction at 175-177°C, and obtain 1.2 g of limonene.
实施例3Example 3
1、将30g废橡胶轮胎和210g甲苯加入高压釜中加热到330℃，4.4MPa压力下恒温恒压40min，得到223.2g柠檬烯混合物。1. Put 30g of waste rubber tires and 210g of toluene into an autoclave and heat to 330°C, keep the temperature and pressure at 4.4MPa for 40min to obtain 223.2g of limonene mixture.
2、将超临界解聚得到的混合物进行蒸馏，收集170～180℃的馏分，得到6.5g柠檬烯粗品。2. Distill the mixture obtained by supercritical depolymerization, collect fractions at 170-180° C., and obtain 6.5 g of crude limonene.
3、再将柠檬烯粗品进行精馏，收集175～177℃的馏分，得2.1g柠檬烯产品。3. Carry out rectification on the crude limonene product, and collect the fraction at 175-177°C to obtain 2.1 g of limonene product.
实施例4Example 4
1、将25g废橡胶轮胎和200g甲苯加入高压釜中加热到330℃，4.5MPa压力下恒温恒压60min，得到211.2g柠檬烯混合物。1. Put 25g of waste rubber tires and 200g of toluene into an autoclave and heat to 330°C, keep the temperature and pressure at 4.5MPa for 60min to obtain 211.2g of limonene mixture.
2、将超临界解聚得到的混合物进行蒸馏，收集170～180℃的馏分，得到5.7g柠檬烯粗品。2. Distill the mixture obtained by supercritical depolymerization, collect fractions at 170-180° C., and obtain 5.7 g of crude limonene.
3、再将柠檬烯粗品进行精馏，收集175～177℃的馏分，得1.5g柠檬烯产品。3. Then rectify the crude limonene product, collect the fraction at 175-177°C, and obtain 1.5 g of limonene product.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100506574A CN100387559C (en) | 2006-04-30 | 2006-04-30 | Method for producing limonene from waste rubber tires |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100506574A CN100387559C (en) | 2006-04-30 | 2006-04-30 | Method for producing limonene from waste rubber tires |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1844068A CN1844068A (en) | 2006-10-11 |
| CN100387559C true CN100387559C (en) | 2008-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100506574A Expired - Fee Related CN100387559C (en) | 2006-04-30 | 2006-04-30 | Method for producing limonene from waste rubber tires |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110938450B (en) * | 2019-12-16 | 2020-10-09 | 华中科技大学 | Method for preparing pyrolysis oil and limonene by pressure pyrolysis of waste tires |
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- 2006-04-30 CN CNB2006100506574A patent/CN100387559C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| F-11 废轮胎和天然橡胶在超临界甲苯中的解聚. 潘志彦，刘银秀，金红茂，林春绵.第三届全国环境化学学术大会论文集. 2005 |
| F-11 废轮胎和天然橡胶在超临界甲苯中的解聚. 潘志彦，刘银秀，金红茂，林春绵.第三届全国环境化学学术大会论文集. 2005 * |
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| CN1844068A (en) | 2006-10-11 |
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