CN1043153A - Prepare the method for petroleum base softening agent and prepared petroleum base softening agent - Google Patents
Prepare the method for petroleum base softening agent and prepared petroleum base softening agent Download PDFInfo
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- CN1043153A CN1043153A CN 88109747 CN88109747A CN1043153A CN 1043153 A CN1043153 A CN 1043153A CN 88109747 CN88109747 CN 88109747 CN 88109747 A CN88109747 A CN 88109747A CN 1043153 A CN1043153 A CN 1043153A
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- softening agent
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Abstract
The present invention is with oil, especially to isolate the high boiling residue behind the petroleum product be raw material to the conventional processing of naphthenic base oil, handling through simple underpressure distillation is the separable petroleum base softening agent of preparing that obtains mainly separating as the method for polyvinylhalide, particularly plasticizer for polyvinyl chloride and with this method.
Description
What the present invention relates to is to separate the method for preparing softening agent the resistates after refining of petroleum and with the prepared petroleum base softening agent of this method.
Contain polyvinylhalide, especially the goods of polyvinyl chloride polymer composition are very extensive and a large amount of at present.Because this resinoid or polymkeric substance self character must be used with suitable softening agent, to improve its processing and use properties.Along with the difference of use properties requirement and the performance characteristics of softening agent itself, the kind of common plasticizers is more, but generally mostly be the softening agent of various organosilane ester structures, especially general needed integrated performance index phthalate (as butyl ester, monooctyl ester etc.) Chang Zuowei primary plasticizer is preferably extensively being used in large quantities.These softening agent mostly are by basic chemical raw materials by special synthetic and produce and to obtain, and therefore, begin till produce product from raw material, and resulting cost is higher.Some industrial chemicals, the needed butanols of butyl ester class softening agent that for example production usage quantity is bigger also will consume a large amount of grain.Therefore people are striving to find new raw materials for production and are opening up the new way of producing softening agent at present.Be raw material with the resistates after the refining of petroleum or other various tar wherein, separation and Extraction effective constituent is also carried out processing treatment and is used as softening agent, as Poland Patent 109124, all has disclosed in French Patent 2202516 and the documents such as 2070026.Especially United States Patent (USP) 3511794 has been introduced in more detail and prepared direct method as polyvinylhalide base polymer softening agent a kind of the separation from the last high boiling residue in oil routine processing back.But the method that these data, especially above-mentioned United States Patent (USP) are introduced all is the product that will carry out just finally being can be used as after furfural extraction-separation solvent-processes such as pressurized catalysis processing-distillation softening agent to raw material.Its shortcoming obviously shows: (1) flow line is oversize; (2) plant and instrument of Xu Yaoing is many and complicated, requires height, and price is expensive; (3) operation skill requires highly, and for example: resemble in this United States Patent (USP) pointedly, the process of removing extraction solvent has only by skilled red-tape operati skill could prevent effectively that the mixture of solvent-extract from taking place to decompose and/or polymerization; (4) needs of, auxiliary material former and reagent to extraction solvent, catalyzer etc. and consume many, and wherein as essential materials such as alditol be not to be all acquisitions easily everywhere yet.The combined influence of these unfavorable factors does not have grain husk has greatly increased the cost of final softening agent product, makes extensively inexpensive this favorable factor of raw material sources most of or exhaust substantially.
It is that raw material separates the main more simple method as polyvinylhalide, particularly plasticizer for polyvinyl chloride of preparation with the resistates after the refining of petroleum that the present invention's purpose at first provides a kind of.
It is that raw material separates the main method as polyvinylhalide, particularly plasticizer for polyvinyl chloride of preparation with the resistates after the naphthenic base oil processing particularly that second purpose of the present invention provides a kind of.
A further object of the present invention provides the softening agent that a kind of usefulness method of the present invention is separated the polyvinylhalide of preparing that is mainly used in, particularly polyvinyl chloride polymer or goods.
The inventive method be with oil routinely the high boiling residue isolated behind the various petroleum products commonly used of cracking and fractionating method be raw material, carry out underpressure distillation under heating condition, the 250-400 ℃ of interior cut of boiling range scope gets final product under the collection 10-80mm.Hg pressure condition.Because the atmospheric boiling point of this scope cut is about 500 ℃, be advisable with underpressure distillation.Because the habitat of oil difference of raw material sources, composition is difference to some extent, isolate impurity components such as various compositions and pitch in the resistates behind the petroleum product commonly used, colloid with ordinary method what are also different.Generally when these impurity levels are no more than 10%, can do special processing, directly adopt aforesaid method of the present invention to carry out underpressure distillation used raw material; If foreign matter content is too much, then, carry out underpressure distillation behind the impurity components such as colloid again and be advisable, otherwise both be unfavorable for steaming of effective constituent to remove most pitch with conventional acid-alkali treatment method earlier, can influence the quality of overhead product again, the difficulty that also causes distillation back resistates to remove simultaneously.
Consider from the performance perspective of softening agent, think more at large that now ring-type hydro carbons, especially various aromatic hydrocarbons compositions are the plasticizing efficiencies that help improving and improve softening agent.Different in the oil ingredient kind of raw material sources and ratio roughly can be divided into oil alkyl group oil and naphthenic base oil two big classes, and wherein the latter's cyclic hydrocarbon constituents proportion is bigger.Therefore when adopting the inventive method, to use the resistates after the naphthenic base oil processing is made raw material for well especially, need not carry out too much separation and Extraction operation, only just can obtain satisfactory product by simple underpressure distillation.To the raw material of different sources,, can repeat again once or the underpressure distillation of identical requirement is for several times made with extra care underproof cut if do not reach specified requirement by the collected cut of underpressure distillation.
Show by the test that the inventive method is carried out, the sulfur-bearing composition in the raw material, or steamed in formal the separation before collecting required cut in advance, or still reside in the distillation residue at last and do not steamed.Thereby generally needn't take as in the furfural extraction method, run into because of having a large amount of sulfur-bearing compositions to be enriched in to have in the extraction solvent desulfurization that increases to handle operation.Not high by sulfocompound composition in the cut of the inventive method collection, generally can not surpass 2%, can meet the requirement of general use fully.
According to aforesaid method of the present invention from oil, particularly from the resistates after the naphthenic base oil processing, separate the petroleum base softening agent of preparing, be actually a kind of complicated ingredient liquid mixture by multiple hydrocarbon composition, wherein the total amount of ring-type hydro carbons should be the 50-95% of gross weight, all the other are chain hydrocarbon and other material, molecular-weight average is 300-350, boiling range 250-400 ℃/10-80mm.Hg, and proportion d
20 4=0.85-1.1,150-210 ℃ of flash-point (open type).As previously mentioned, ring-type hydro carbons, the especially increase of aromatic hydrocarbons composition help improving the plasticising performance of softening agent, and therefore the content requirement that the ring-type hydro carbons is necessary by the prepared softening agent of the inventive method has enough good plasticizing efficiency with assurance.Because in said ring-type hydro carbons, aromatic hydrocarbons generally all occupies significant proportion, or even has comparative advantage, therefore when guaranteeing that total ring-type hydrocarbon content reaches requirement, the shared ratio of aromatic hydrocarbons has also just met the requirements.Generally speaking, when being raw material for the resistates that adopts naphthenic base oil, through once or a small amount of limited resulting cut of underpressure distillation several times requirement of reaching petroleum base softening agent of the present invention be difficulty.If because of total naphthene content in the raw material cross low cause through distill repeatedly, separate inaccessible softening agent of the present invention still require standard the time, this raw material then should not adopt, or also must make the methods such as catalytic hydrogenation introduced in the above-mentioned reference data of the processing of others-for example-just can reach the requirement of the said petroleum base softening agent of the present invention after the performance index of improving total ring-type hydrocarbon content and other aspect.
Say objectively, because the performance requriements to the relevant goods of various different uses field and scope varies, therefore still do not have at present, also can not have and can satisfy all use propertieies requirement and every performance index all well-content " all-round " type softening agent, and can only be according in most cases general some main performance index are made comprehensive evaluation to the quality of certain softening agent.Petroleum base softening agent provided by the present invention also is like this.Because total ring-type hydro carbons in the softening agent of the present invention, especially the content of aromatic hydrocarbons is higher, plasticization effect is fine, so under the prerequisite that the different use propertieies of plasticising object goods require satisfying, both can use petroleum base softening agent of the present invention separately, also can with the softening agent of other type, cooperate the back to use as softening agent such as various organosilane esters, epoxy compounds classes.When being used, generally has good intermiscibility between softening agent of the present invention and other softening agent.Consider that from the over-all properties of improving, adjust and improve plasticization effect yes to adopt a kind of mode in back to use more favourable.Compare with present widely used phthalic ester (as butyl ester, monooctyl ester etc.) class primary plasticizer, petroleum base softening agent of the present invention not only also has integrated performance index characteristics preferably, and also has the distinguishing feature that some are better than these primary plasticizers in some aspects.For example experiment shows, use petroleum base softening agent of the present invention after, the flow influence of property relaxes when using above-mentioned ester plasticizer than simple to the goods mixture to make temperature, processing temperature is easy to control.To the plasticizing efficiency height of the common goods of general requirement, the surface luster property of goods is better, elasticity, insulativity, volatility, anti-extractibility, wear resistance, winter hardiness and the each side such as stability of light, heat are all had improving in various degree.For example the 70 ℃ of CABLE MATERIALS of polyvinyl chloride that adopt elasticizer plasticizing of the present invention are done the cable sheath test, except that on general property indexs such as tensile strength, elongation at break, heat-stable time and thermal ageing rate, all reaching or being higher than the requirement standard, aspect electrical property, also shown its outstanding advantage especially, can reach 10 as specific resistance
13(ohm, centimetre) more than, voltage breakdown is higher than 31 kvolts/millimeter etc.With the exception of this, the use range of softening agent of the present invention even can expand to outside the polyvinylhalide class.For example with petroleum base softening agent of the present invention natural rubber is made oil-filled industrial amplification test, the sizing material after oil-filled is at heat-resisting, anti-ozone, sun-resistant aging, and the performance of aspects such as Akron abrasion and freedom from cracking all has bigger improvement.
On the other hand, petroleum base of the present invention is moulded agent and be that the result that the primary plasticizer of representative carries out the acute toxicity contrast experiment is: medium lethal dose (LD with the dibutyl phthalate
50) the former is 8.044, the latter is 6.248(gram/kilogram), shown that the former toxicity is starkly lower than the latter.Plasticizer volatility of the present invention in addition is low, and therefore several no any smells in production and processing, use have more improved the safety and reliability of this product.This shows.No matter be on the plasticising performance, or the toxicity aspect, petroleum base softening agent of the present invention not only can be used with this class primary plasticizer, and can replace this class primary plasticizer to a great extent.Even must use under the situation of this class primary plasticizer, also can do substituting of part, and the alternate ratio be the highest even can reach about 70%.
Prepare from separation provided by the present invention on the method for this petroleum base softening agent, because general need be the separable the finished product that obtain through simple underpressure distillation operation only, saved the solvent extraction of taking at present, operation stepss such as pressurized catalysis processing, flow line shortens dramatically, the consumption of required equipment, instrument and raw and auxiliary material, reagent and process cost etc. also all correspondingly reduce undoubtedly significantly, have also avoided for want of certain reagent or material simultaneously and to producing the disadvantageous effect that is caused.Remove raw material inexpensive outside, these can further reduce the cost of petroleum base softening agent of the present invention.Compare with aforesaid primary plasticizer, cost can reduce 60-70% approximately.And with some have the softening agent ratio of property at present, the cost fall is bigger, for example compares with some cold-resistant plasticizer, and cost can reduce 70-80%, and softening agent of the present invention has cold tolerance preferably equally.Be worth especially pointing out that different with present a large amount of primary plasticizers that use is, production softening agent of the present invention does not consume grain fully, and this is to have the meaning that is even more important.With the exception of this, softening agent of the present invention is to separate the resistates after refining of petroleum to prepare, and in separating preparation process, do not have the new three wastes again and produce, so not only alleviated the problem of environmental pollution in the refining of petroleum to a certain extent, and further enlarged development and use scope to petroleum resources, become original waste and be useful thing, developed a kind of well behaved softening agent kind.
By the following specific embodiment of introducing, can further make more clear detailed explanation to content of the present invention.
Operating process: oil is processed in the high boiling residue raw material input decompression still of isolating behind the petroleum products routinely, and the cut of specified pressure and boiling range scope is collected in straight fire heating carrying out underpressure distillation.If when underpressure distillation products obtained therefrom does not reach the whole standard-required of petroleum base softening agent of the present invention as yet, generally can carry out underpressure distillation once more to this cut by same operation and requirement.
Example 1: (gum level (10%) is collected 250-400 ℃/20-80mm.Hg cut, products obtained therefrom proportion d to the oily raw material of the three-way extraction of Yumen refinery
20 4=0.96-1, molecular-weight average is about 350, wherein total naphthenic hydrocarbon 20.5%, 1-4 Polycyclic aromatic hydrocarbons total amount 66.8%, total thiophene 1.9%, open flash point 170-200 ℃.
Example 2: huge port refinery second line of distillation is raffinated oil, and (gum level (10%) is collected 300-360 ℃/40-80mm.Hg cut to raw material.The every index of product is qualified.
Claims (5)
1, a kind of with oil routinely the resistates that separates behind the petroleum products commonly used of working method be that raw material separates the method for preparing the petroleum base softening agent, it is characterized in that raw material heating and carry out underpressure distillation, be collected in the cut of 250-400 ℃ of boiling range scope under the 10-80mm.Hg pressure condition.
2, the method for claim 1 is characterized in that said raw material is from the resistates of naphthenic base oil being processed after the separation.
3, a kind of with oil routinely the resistates that separates behind the petroleum products commonly used of working method be raw material, separate the petroleum base softening agent of preparing through underpressure distillation, it is characterized in that it is that a kind of boiling range is the oily liquids mixture of 250-400 ℃/10-80mm.Hg, wherein the ring-type hydro carbons accounts for 50-95%(weight), all the other are chain hydrocarbon and impurity, molecular-weight average is 300-350, proportion d
20 4=0.85-1.1,150-210 ℃ of flash-point (open type).
4, petroleum base softening agent as claimed in claim 3 is characterized in that being is that raw material separates the product for preparing with the resistates from naphthenic base oil.
5,, it is characterized in that said ring-type hydro carbons is an aromatic hydrocarbons as claim 3 or 4 described petroleum base softening agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88109747 CN1043153A (en) | 1988-11-28 | 1988-11-28 | Prepare the method for petroleum base softening agent and prepared petroleum base softening agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88109747 CN1043153A (en) | 1988-11-28 | 1988-11-28 | Prepare the method for petroleum base softening agent and prepared petroleum base softening agent |
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| CN1043153A true CN1043153A (en) | 1990-06-20 |
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| CN 88109747 Pending CN1043153A (en) | 1988-11-28 | 1988-11-28 | Prepare the method for petroleum base softening agent and prepared petroleum base softening agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397377B (en) * | 2007-09-25 | 2012-11-21 | Sk新技术株式会社 | Auxiliary plasticizers of PVC and PVC sol composition and products containing the same |
| CN103524920A (en) * | 2013-08-15 | 2014-01-22 | 江苏隆昌化工有限公司 | Recycled chlorinated arene waste for replacing PVC (polyvinyl chloride) plasticizer |
| CN105907421A (en) * | 2016-06-21 | 2016-08-31 | 中国海洋石油总公司 | Preparing method for low-viscosity environment-friendly rubber oil |
| CN106010638A (en) * | 2016-06-21 | 2016-10-12 | 中国海洋石油总公司 | Preparation method of low-viscosity green rubber plasticizer |
| CN108424784A (en) * | 2018-04-17 | 2018-08-21 | 连云港鹏辰特种新材料有限公司 | A method of the continuous aromatics separation plasticizer from mixing C+10 heavy aromatic hydrocarbon |
-
1988
- 1988-11-28 CN CN 88109747 patent/CN1043153A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397377B (en) * | 2007-09-25 | 2012-11-21 | Sk新技术株式会社 | Auxiliary plasticizers of PVC and PVC sol composition and products containing the same |
| CN103524920A (en) * | 2013-08-15 | 2014-01-22 | 江苏隆昌化工有限公司 | Recycled chlorinated arene waste for replacing PVC (polyvinyl chloride) plasticizer |
| CN105907421A (en) * | 2016-06-21 | 2016-08-31 | 中国海洋石油总公司 | Preparing method for low-viscosity environment-friendly rubber oil |
| CN106010638A (en) * | 2016-06-21 | 2016-10-12 | 中国海洋石油总公司 | Preparation method of low-viscosity green rubber plasticizer |
| CN105907421B (en) * | 2016-06-21 | 2017-08-29 | 中国海洋石油总公司 | A kind of preparation method of low-viscosity environment-friendly rubber oil |
| CN108424784A (en) * | 2018-04-17 | 2018-08-21 | 连云港鹏辰特种新材料有限公司 | A method of the continuous aromatics separation plasticizer from mixing C+10 heavy aromatic hydrocarbon |
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