CN101693772B - Method for producing environment-friendly rubber oil through blending method - Google Patents
Method for producing environment-friendly rubber oil through blending method Download PDFInfo
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- CN101693772B CN101693772B CN2009102364196A CN200910236419A CN101693772B CN 101693772 B CN101693772 B CN 101693772B CN 2009102364196 A CN2009102364196 A CN 2009102364196A CN 200910236419 A CN200910236419 A CN 200910236419A CN 101693772 B CN101693772 B CN 101693772B
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Abstract
The invention discloses a method for producing environment-friendly rubber oil through blending method. The method provided by the invention comprises the following steps that firstly extracting decompressed residual oil with solvent to obtain deasphalted oil, wherein the solvent for extraction is propane, the ratio by volume of the solvent and the decompressed residual oil is (6-8):1, and the extraction conditions are that the temperature of a tower top is 60-95 DEG C, the temperature of a tower bottom is 50-80 DEG C, and the pressure is 2.8-7.0 MPa, secondly mixing deasphalted oil obtained in the first step with naphthenic oil for 30-120 min with 70-90 DEG C to obtain environment-friendly rubber oil, wherein the mass ratio of the deasphalted oil and the naphthenic oil is (0.2-0.6):(0.8-0.4). The environment-friendly rubber oil produced by the invention accords with the environment-friendly instruction requirement of EU 2005/69/EC, wherein aromatic-carbon rate is 12%-18%, the contentof PCA is smaller than 3%, the content of aromatic hydrocarbons is high, and the rubber oil is environment-friendly, nontoxic, and has no carcinogenic effect. The environment-friendly rubber oil can be used as succedaneum of existing aromatic oil, and has great economic values.
Description
Technical field
The present invention relates to a kind of method of producing environment-friendly rubber oil through blending method.
Background technology
At present, polycyclc aromatic compound (being called for short PCA) has become countries in the world environmental protection and the common organic pollutant of paying close attention to of normal structure.Widely used aromatic hydrocarbon oil contains a large amount of these type of materials in rubber and tire industry, and the human body environment has all been caused harm.According to the 2005/69/EC instruction of European Union signature,, enter in the tire in European Union market and will completely forbid the deleterious aromatic hydrocarbon oil of use from January 1st, 2010.The U.S. and Japan have also all formulated the timetable that uses aromatic hydrocarbon oil and forbid selling in this zone this oil product tire of use in the tire that is limited in.Therefore, each exports tyre production enterprise and is actively preparing the replacement aromatic hydrocarbon oil, uses environment-friendly rubber oil instead.
Current environment-friendly rubber oil production technology mainly contains two kinds: hydrofining or solvent treatment.Usually, the environment-friendly rubber oil of hydrofining production is easy to satisfy environmental protection index, but because therefore a large amount of saturated the or generation cracking of aromatic hydrocarbons quilt in the hydrogenation process are difficult to produce the product of performance near aromatic hydrocarbon oil, the use value of the finished product is limited greatly.Solvent treatment can well realize the selective separation of aromatic hydrocarbons, therefore be the main flow production method of the environment-friendly rubber oil supplied on the current market, product mainly comprises TDAE and TRAE, concrete production principle is that by solvent distillate or residual oil raw material to be carried out repeatedly extracting refining, obtain useful single double ring arene in the oil product, and remove wherein toxic substances such as polycyclic aromatic hydrocarbons, make the finished product keep higher aromaticity content, the aromatic carbon rate C of product
ACan reach 25%, performance and aromatic hydrocarbon oil are comparatively approaching.But because method for refining solvent need repeatedly be handled raw material usually, product yield is lower, and tooling cost is very high, and operational condition is required also comparatively harshness, and therefore supply is difficult to meet the need of market, and valuable product.
Current, domestic is that the Rubber processing of representative already develops rapidly with the tire production, and the demand of rubber oil is also being risen year by year.Wherein, the tire that section port is gone abroad is because the necessary environment-friendly rubber oil that uses is therefore extremely urgent to the demand of environment-friendly rubber oil.But the main dependence on import of this series products costs an arm and a leg at present, and supply is difficult to ensure.Therefore, develop cheap environment-friendly rubber oil production, widen the environment-friendly rubber oil supplying, have great economic worth and social effect.
Summary of the invention
The method that the purpose of this invention is to provide a kind of producing environment-friendly rubber oil through blending method.
The production method of environment-friendly rubber oil provided by the invention comprises the steps:
1) vacuum residuum is carried out solvent extraction, obtain deasphalted oil;
The used solvent of described extracting is a propane; The volume ratio of described solvent and described vacuum residuum is (6-8): 1; Described extractive condition is: tower top temperature is 60-95 ℃, and column bottom temperature is 50-80 ℃, and pressure is 2.8-7.0Mpa;
2) deasphalted oil that step 1) is obtained mixes 30-120min with naphthenic oil 70-90 ℃, obtains environment-friendly rubber oil; The mass ratio of described deasphalted oil and described naphthenic oil is (0.2-0.6): (0.8-0.4).
Described vacuum residuum can be Zhong Hai Suizhong 36-1 vacuum residuum; Described naphthenic oil can be CNOOC's naphthenic oil.
The environment-friendly rubber oil that described method prepares also belongs to protection scope of the present invention.
The preparation flow synoptic diagram of environment-friendly rubber oil of the present invention is seen Fig. 1.
Environment-friendly rubber oil properties of the present invention sees Table 1.
The environment-friendly rubber oil properties that table 1 adopts method of the present invention to prepare
Environment-friendly rubber oil of the present invention has the following advantages:
1, aromaticity content height.Aromatic carbon rate C
AValue can reach 12%-18%, and product aromaticity content height of the present invention is described, and is good with the consistency of rubber, uses in tire production, more can give tire good high-performances such as anti-slippery.
2, nontoxic, no carcinogenesis.Product of the present invention satisfies the qualifications among the european union directive 2005/69/EC: the content of polynuclear aromatic compound (PCA) is less than 3%, and the content of benzopyrene is less than 1ppm, and the total content of 8 kinds of condensed-nuclei aromaticss is less than 10ppm.
3, raw material is easy to get.Above-mentioned raw materials is the commercially available prod of China National Offshore Oil Corporation (CNOOC), has good commercial exploitation prospect.
The present invention is a raw material with the vacuum residuum of cheapness, by solvent deasphalting, controls suitable yield, refines to obtain deasphalted oil, produces environment-friendly rubber oil by concocting with naphthenic oil again.Raw materials cost is lower, and operational condition relaxes, and the finished product cost is relatively low, is a kind of novel method of producing environment-friendly rubber oil.Environment-friendly rubber oil of the present invention meets the 2005/69/EC of European Union environmental protection command request, and the aromatic carbon rate is 12%-18%, and the content of PCA is less than 3%, aromaticity content height, environmental protection, nontoxic, no carcinogenesis.Environment-friendly rubber oil of the present invention can be used as the substitute of existing aromatic hydrocarbon oil, has great economic worth.
Description of drawings
Fig. 1 is the preparation flow synoptic diagram of environment-friendly rubber oil of the present invention.
Embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Experimental technique among the following embodiment if no special instructions, is ordinary method.Used test materials among the following embodiment if no special instructions, is to buy from routine biochemistry reagent shop and obtains.In following examples, if no special instructions, " % " all refers to the quality percentage composition.Revision test all is set three times, results averaged among the embodiment.
Vacuum residuum (Zhong Hai Suizhong 36-1 vacuum residuum): bitumen A H-200, Zhonghai Pitch Co., Ltd sells.CNOOC's naphthenic oil: general naphthenic base oils; Zhonghai Pitch Co., Ltd sells.
The preparation flow of the environment-friendly rubber oil in following examples is referring to Fig. 1.
The preparation of embodiment 1, environment-friendly rubber oil and property testing
1) is raw material with Zhong Hai Suizhong 36-1 vacuum residuum, in extraction tower, carries out extracting and obtain deasphalted oil; The extracting condition is: tower top temperature is 95 ℃, and column bottom temperature is 80 ℃, and solvent is a propane, and the volume ratio of solvent and Zhong Hai Suizhong 36-1 vacuum residuum is 8: 1, and working pressure is 2.8Mpa.
2) deasphalted oil that step 1) is obtained and naphthenic oil fully mix 30min by under 70 ℃ in the mixing tank, obtain environment-friendly rubber oil; Deasphalted oil and naphthenic oil mass ratio are 0.6: 0.4.
The environment-friendly rubber oil properties sees Table 2.
The environment-friendly rubber oil properties of table 2 embodiment 1 preparation
As can be seen from the table, the C of environment-friendly rubber oil of the present invention
AValue is 12%, therefore, has certain aromatic hydrocarbon content, in use can be better with the consistency of rubber, and processing characteristics also can be better.Secondly, its PCA content is 2.3%, is far smaller than the content 3% of regulation, illustrates that environment-friendly rubber oil of the present invention is nontoxic no carcinogenesis.
The preparation of embodiment 2, environment-friendly rubber oil and property testing
1) is raw material with Zhong Hai Suizhong 36-1 vacuum residuum, in extraction tower, carries out extracting and obtain deasphalted oil; The extracting condition is: tower top temperature is 80 ℃, and column bottom temperature is 65 ℃, and solvent is a propane, and the volume ratio of solvent and Zhong Hai Suizhong 36-1 vacuum residuum is 6: 1, and working pressure is 4.8Mpa.
2) deasphalted oil that step 1) is obtained and naphthenic oil fully mix 120min by under 80 ℃ in the mixing tank, obtain environment-friendly rubber oil; Deasphalted oil and naphthenic oil mass ratio are 0.5: 0.5.
The environment-friendly rubber oil properties sees Table 3.
The environment-friendly rubber oil properties of table 3 embodiment 2 preparations
As can be seen from the table, the C of environment-friendly rubber oil of the present invention
AValue is 18%, therefore, has very high aromatic hydrocarbon content, in use can be better with the consistency of rubber, and processing characteristics also can be better.Secondly, its PCA content is 2.7%, and the content 3% less than regulation illustrates that environment-friendly rubber oil of the present invention is nontoxic no carcinogenesis.
The preparation of embodiment 3, environment-friendly rubber oil and property testing
1) is raw material with Zhong Hai Suizhong 36-1 vacuum residuum, in extraction tower, carries out extracting and obtain deasphalted oil; The extracting condition is: tower top temperature is 60 ℃, and column bottom temperature is 50 ℃, and solvent is a propane, and the volume ratio of solvent and Zhong Hai Suizhong 36-1 vacuum residuum is 8: 1, and working pressure is 7.0Mpa.
2) deasphalted oil that step 1) is obtained and naphthenic oil fully mix 90min by under 90 ℃ in the mixing tank, obtain environment-friendly rubber oil; Deasphalted oil and naphthenic oil mass ratio are 0.2: 0.8.
The environment-friendly rubber oil properties sees Table 4.
The environment-friendly rubber oil properties of table 4 embodiment 3 preparations
As can be seen from the table, the C of environment-friendly rubber oil of the present invention
AValue is 16%, therefore, has very high aromatic hydrocarbon content, in use can be better with the consistency of rubber, and processing characteristics also can be better.Secondly, its PCA content is 2.6%, and the content 3% less than regulation illustrates that environment-friendly rubber oil of the present invention is nontoxic no carcinogenesis.
Claims (2)
1. the production method of an environment-friendly rubber oil comprises the steps:
1) vacuum residuum is carried out solvent extraction, obtain deasphalted oil;
The used solvent of described extracting is a propane; The volume ratio of described solvent and described vacuum residuum is (6-8): 1; Described extractive condition is: tower top temperature is 60-95 ℃, and column bottom temperature is 50-80 ℃, and pressure is 2.8-7.0Mpa;
2) deasphalted oil that step 1) is obtained mixes 30-120min with naphthenic oil 70-90 ℃, obtains environment-friendly rubber oil; The mass ratio of described deasphalted oil and described naphthenic oil is (0.2-0.6): (0.8-0.4);
Described vacuum residuum is Zhong Hai Suizhong 36-1 vacuum residuum; Described naphthenic oil is CNOOC's naphthenic oil.
2. the environment-friendly rubber oil for preparing of the described method of claim 1.
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| CN105542487B (en) * | 2016-01-29 | 2018-03-06 | 华东理工大学 | A kind of rapid-curing cutback mist sealing material and its production and use |
| CN115651288B (en) * | 2022-11-15 | 2024-01-26 | 中国海洋石油集团有限公司 | High C A Rubber plasticizer with value and preparation method thereof |
| CN116622248A (en) * | 2023-06-15 | 2023-08-22 | 成都大兰农民投资股份有限公司 | Production method of rubber plasticizer-aromatic base mineral oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2218379C2 (en) * | 2001-10-03 | 2003-12-10 | Открытое акционерное общество "Славнефть-Ярославнефтеоргсинтез" | Oil residue deasphalting process |
| RU2235110C1 (en) * | 2002-11-29 | 2004-08-27 | Нигматуллин Виль Ришатович | Two-step process for propane deasphalting of vacuum residues |
| CN101386687A (en) * | 2008-10-24 | 2009-03-18 | 中国海洋石油总公司 | Aromatic rubber oil and producing method thereof |
| CN101495559A (en) * | 2006-07-26 | 2009-07-29 | 出光兴产株式会社 | Treatment oil for rubber |
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- 2009-10-21 CN CN2009102364196A patent/CN101693772B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2218379C2 (en) * | 2001-10-03 | 2003-12-10 | Открытое акционерное общество "Славнефть-Ярославнефтеоргсинтез" | Oil residue deasphalting process |
| RU2235110C1 (en) * | 2002-11-29 | 2004-08-27 | Нигматуллин Виль Ришатович | Two-step process for propane deasphalting of vacuum residues |
| CN101495559A (en) * | 2006-07-26 | 2009-07-29 | 出光兴产株式会社 | Treatment oil for rubber |
| CN101386687A (en) * | 2008-10-24 | 2009-03-18 | 中国海洋石油总公司 | Aromatic rubber oil and producing method thereof |
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Effective date of registration: 20170221 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: China National Offshore Oil Corporation Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: China National Offshore Oil Corporation Patentee before: China National Offshore Oil and Gas Development and Utilization Co., Ltd. |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: China National Offshore Oil Corporation Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: China National Offshore Oil Corporation Patentee before: China National Offshore Oil Corporation Co-patentee before: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. |
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