CN103805220B - A kind of preparation method of high softening point bitumen - Google Patents
A kind of preparation method of high softening point bitumen Download PDFInfo
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- CN103805220B CN103805220B CN201210439793.8A CN201210439793A CN103805220B CN 103805220 B CN103805220 B CN 103805220B CN 201210439793 A CN201210439793 A CN 201210439793A CN 103805220 B CN103805220 B CN 103805220B
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Abstract
The invention discloses a kind of preparation method of high soft spots pitch.The method comprises following content: pitch and the oxygenant of molten state spray into oxidation reactor respectively simultaneously, carry out oxidizing reaction, obtain high softening point bitumen.Wherein oxygenant is nano level potassium permanganate and/or nano level potassium bichromate, by high-pressure pump and compress wind pitch and oxygenant respectively with mist state, spray into oxidation reactor simultaneously and mix.The inventive method oxygenant consumption is less, oxidizing temperature is low, reaction efficiency is high, easy to operate, and reaction process environmental friendliness, energy consumption is low.
Description
Technical field
The present invention relates to a kind of preparation method of high softening point bitumen, relate in particular to a kind of efficient oxidation method utilizing oxygenant to prepare high softening point bitumen.
Background technology
High softening point bitumen refers to that softening temperature is more than 100 DEG C, the pitch especially more than 120 DEG C.High softening point bitumen has because of its outstanding high-temperature resistance to be applied more widely.As the use of the roof cover as building, even trickle even if also can not become very soft during the broiling summer.Can also be used in the drilling operation in deep-seated oil gas field, as the important component part of drilling fluid, shutoff, anti-collapse, stabilizing borehole can be played under the high temperature conditions, reduce the effect of filter loss.In addition, property-modifying additive of macromolecular material etc. can also be used as.
High softening point bitumen production technique mainly adopts solvent de-asphalting process or oxidizing process.According to existing solvent de-asphalting process, produce high softening point bitumen, need to adopt heavier solvent.For remove pitch mutually in solvent, need be heated to higher temperature, very easily cause the problems such as furnace coking, and energy consumption is very large.In addition, even if the viscosity of high softening point bitumen is still very large at a higher temperature, production equipment discharging is also more difficult, therefore current solvent de-asphalting process not very suitable for producing high softening point bitumen.
Oxidized bitumen technique refers to softening temperature low, the vacuum residuum that penetration degree is large and temperature sensitivity is high, solution-off pitch or their mixture are raw material, in oxidizing tower, under certain temperature condition, pass into air (making oxygenant with oxygen) react, make it form to change, softening temperature raises, penetration degree and temperature sensitivity decline, to reach the requirement of asphaltic products. specification and use properties.The advantages such as compared with solvent de-asphalting process, oxidizing process has less investment, and technique is simple, easy to operate, can yet be regarded as and produce the comparatively ideal process means of high softening point bitumen.
But, in traditional oxidized bitumen technological operation, be that pressurized air is imported in raw material by an air distribution ring with very thin nozzle, utilize the oxygen in air to make oxygenant and carry out oxidized bitumen.But, owing to only having small part to be oxygen in air, and major part be nitrogen and other can not carry out the rare gas element of chemical reaction with pitch.Oxygen level is low on the one hand affects oxidation efficiency, on the one hand a large amount of nitrogen can not occupy again large quantity space with the rare gas element that pitch carries out chemical reaction with other and pitch fully can not be contacted with oxygen, partial oxidation is not fully utilized, and the oxidation efficiency of pitch is decreased again.Being that necessity passes into large quantity of air to make pitch fully oxidized, not participating in the production process that the nitrogen of chemical reaction and other rare gas element inevitably participate in pitch on the one hand in a large number, greatly wasting energy; The nitrogen that can not be utilized in a large number on the one hand and rare gas element carry again the part produced in pitch oxidation process and are harmful to together with light constituent and are discharged in air, cause topsoil again.It is low that this not only causes efficiency, polluted air, and reaction is also very uneven.In fact, reaction only occurs bottom oxidizing tower.
In order to solve the problems referred to above existed in pitch oxidation process, Austrian Po Neng company discloses a kind of BITUROX technique, and it is in oxidizing tower, add three grades of whipping apptss.Become in large process in bubble rising, blended, again form small bubbles and be distributed in raw material, thus improve oxidation efficiency.This method not only increases the complicacy of mechanical means, increases energy consumption, also brings certain difficulty to overhaul of the equipments.
CN1415699A discloses a kind of production method of oxidized bitumen, first adopts static mixer by air and pitch mixing, makes air with small air bubbles dispersion in asphalt stock, then enter oxidation unit and carry out oxidizing reaction.When production ordinary road pitch and building asphalt, the method can improve oxidation efficiency to a certain extent.But for production high softening point bitumen, this kind of technique also exists obvious deficiency.Because the mixing temperature at static mixer Raw and air is oxidizing temperature, and produce high softening point bitumen and will carry out at a higher temperature.Mix under such temperature conditions, the air bubbles dispersion of seldom amount can only be had in raw material, therefore will be very limited to the degree improving oxidation efficiency, and yet there is air pollution problems inherent.
In order in lower temperature of reaction with in the shorter reaction times, obtain the pitch that softening temperature is high, usually adopt the method for catalyzed oxidation, namely add a certain amount of catalyzer in the reaction, reduce temperature of reaction and improve speed of response.But for production high softening point bitumen, catalyzed oxidation temperature still higher, need oxidization time still long.CN102464989A discloses a kind of premixed catalysed oxidation processes and produces high softening point bitumen, and catalyzer used is zinc oxide, cupric sulfide, iron trichloride and polyphosphoric acid, improves quality and the efficiency of oxidized bitumen product.But oxidising process is comparatively complicated, and oxidizing temperature is still higher.CN102363731A discloses a kind of method improving pitch softening point, gas blower is utilized to send into reactor from the bottom of reactor by oxygenant, pitch melting is carried out to the mode of high-speed and high-temperature oxidation, rapid flash and emulsify at a high speed, obtain the pitch with high softening-point.But the method complicated process of preparation, temperature of reaction are high, and do not write the softening point range of high softening point bitumen exactly.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of high softening point bitumen, the method oxygenant consumption be less, oxidizing temperature is low, reaction efficiency is high, easy to operate, and reaction process environmental friendliness, energy consumption is low.
The preparation method of high soft spots pitch of the present invention, comprises following content: pitch and the oxygenant of molten state spray into oxidation reactor respectively simultaneously, carry out oxidizing reaction, obtain high softening point bitumen.
In the inventive method, pitch is petroleum pitch, comprise vacuum residuum, de-oiled asphalt that straight-run pitch, solvent de-asphalting process obtain, the mixture of one or more that is in harmonious proportion in pitch etc., 25 DEG C of penetration degrees of pitch are 20 ~ 200 1/10mm, and softening temperature is 30 ~ 75 DEG C.
In the inventive method, oxygenant is nano level potassium permanganate and/or nano level potassium bichromate, and its particle diameter is 10 ~ 100nm, and the add-on of oxygenant accounts for 0.5% ~ 10% of asphalt quality.
In the inventive method, by high-pressure pump and compress wind pitch and oxygenant respectively with mist state, spray into oxidation reactor simultaneously, make its full and uniform mixing.Wherein the working pressure of high-pressure pump is 0.2 ~ 2MPa, and compress wind working pressure is 0.2 ~ 1MPa.
In the inventive method, oxidizing temperature is 200 ~ 240 DEG C, and oxidization time is 2 ~ 10 hours.Oxidizing reaction is carried out in a shear condition, and shears rotating speed is 3000 ~ 6000rpm.
The softening temperature of high softening point bitumen product prepared by the inventive method is at 120 ~ 200 DEG C
The inventive method compared with prior art, has the following advantages:
(1) high-pressure pump and compress wind is utilized to be mixed with oxygenant by pitch, the dispersion effect of oxidizing agent pellets in pitch medium is better, under the effect of high-shear, make oxidizing reaction more even, decrease oxygenant consumption, improve quality and the oxidation efficiency of oxidation products.
(2) utilize nano level high-efficient oxidant to be oxidized pitch, its great specific surface area and high surfactivity effect thereof reduce oxidizing temperature in pitch oxidation process, and make oxidizing reaction more abundant, reaction efficiency is high simultaneously.
(3) do not need the air passed into needed for oxidizing reaction, decrease the pollution of waste gas to air, save the use of air compressor etc. and attached air feed equipment thereof simultaneously, make that technical process and equipment are simpler, more convenient operation.
Embodiment
Below will the present invention will be further described by embodiment, but therefore do not limit the present invention.Percentage ratio is wherein massfraction.
Comparative example 1
Be 41 1/10mm by 25 DEG C of penetration degrees, softening temperature is the pitch of 54.6 DEG C, accounts for 96.7% of total amount, be heated to 150 DEG C of molten states, add the polyphosphoric acid of 3.3% and pass into air, shear 25 minutes with high shearing mixing emulsor, enter in oxidizing tower and carry out air blowing oxidation, obtain oxidized bitumen.Oxidation reaction condition and product property are in table 1.
Comparative example 2
Be 41 1/10mm by 25 DEG C of penetration degrees, softening temperature is the pitch of 54.6 DEG C, is heated to 150 DEG C of molten states, adds the common potassium permanganate (taking asphalt quality as benchmark) that particle diameter is 1-2mm, carries out oxidizing reaction, obtain oxidized bitumen.Oxidation reaction condition and product property are in table 1.
Embodiment 1
Be 41 1/10mm by 25 DEG C of penetration degrees, the potassium permanganate of softening temperature to be the pitch of 54.6 DEG C and particle diameter be 50nm uses high-pressure pump and compress wind respectively, sprays into oxidation reactor simultaneously, make its full and uniform mixing carry out oxidizing reaction, obtain oxidized bitumen with mist state.The working pressure of high-pressure pump is 0.8MPa, and compress wind working pressure is 0.5MPa.Oxidizing reaction is carried out in a shear condition, and shears rotating speed is 4000rpm.Oxidation reaction condition and product property are in table 1.
Embodiment 2
Be 41 1/10mm by 25 DEG C of penetration degrees, the potassium permanganate of softening temperature to be the pitch of 54.6 DEG C and particle diameter be 50nm uses high-pressure pump and compress wind respectively, sprays into oxidation reactor simultaneously, make its full and uniform mixing carry out oxidizing reaction, obtain oxidized bitumen with mist state.The working pressure of high-pressure pump is 1.5MPa, and compress wind working pressure is 0.8MPa.Oxidizing reaction is carried out in a shear condition, and shears rotating speed is 3000rpm.Oxidation reaction condition and product property are in table 1.
Embodiment 3
Be 121 1/10mm by 25 DEG C of penetration degrees, the potassium bichromate of softening temperature to be the pitch of 41.8 DEG C and particle diameter be 75nm uses high-pressure pump and compress wind respectively, sprays into oxidation reactor simultaneously, make its full and uniform mixing carry out oxidizing reaction, obtain oxidized bitumen with mist state.The working pressure of high-pressure pump is 2MPa, and compress wind working pressure is 1MPa.Oxidizing reaction is carried out in a shear condition, and shears rotating speed is 6000rpm.Oxidation reaction condition and product property are in table 1.
Embodiment 4
Be 121 1/10mm by 25 DEG C of penetration degrees, the potassium permanganate of softening temperature to be the pitch of 41.8 DEG C and particle diameter be 75nm uses high-pressure pump and compress wind respectively, sprays into oxidation reactor simultaneously, make its full and uniform mixing carry out oxidizing reaction, obtain oxidized bitumen with mist state.The working pressure of high-pressure pump is 2MPa, and compress wind working pressure is 1MPa.Oxidizing reaction is carried out in a shear condition, and shears rotating speed is 6000rpm.Oxidation reaction condition and product property are in table 1.
Table 1 oxidation reaction condition and oxidate product properties.
| Embodiment | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Oxidizing temperature, DEG C | 290 | 235 | 220 | 235 | 230 | 235 |
| Oxidization time, h | 8 | 8 | 3 | 8 | 9 | 10 |
| Air quantity, m 3×kg -1×h -1 | 0.18 | |||||
| Oxidant content (taking asphalt quality as benchmark), % | 10 | 10 | 1 | 8 | 10 | |
| Softening temperature, DEG C | 120 | 121.5 | 120.1 | 135 | 165.8 | 195 |
As can be seen from the data of table 1, the oxidation efficiency of high softening point bitumen prepared by the inventive method is high, and oxidation effectiveness is good, and oxygenant consumption is few.
Claims (8)
1. a preparation method for high softening point bitumen, is characterized in that comprising following content: pitch and the oxygenant of molten state spray into oxidation reactor respectively simultaneously, carry out oxidizing reaction, obtain high softening point bitumen; Wherein said oxygenant is nano level potassium permanganate and/or nano level potassium bichromate; By high-pressure pump and compress wind pitch and oxygenant respectively with mist state, spray into oxidation reactor simultaneously, make its full and uniform mixing.
2. in accordance with the method for claim 1, it is characterized in that: pitch is petroleum pitch, comprise vacuum residuum, de-oiled asphalt that straight-run pitch, solvent de-asphalting process obtain and the mixture of one or more that is in harmonious proportion in pitch.
3. in accordance with the method for claim 1, it is characterized in that: 25 DEG C of penetration degrees of pitch are 20 ~ 2001/10mm, and softening temperature is 30 ~ 75 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: oxygenant is nano level potassium permanganate and/or nano level potassium bichromate, and its particle diameter is 10 ~ 100nm, and the add-on of oxygenant accounts for 0.5% ~ 10% of asphalt quality.
5. in accordance with the method for claim 1, it is characterized in that: the working pressure of high-pressure pump is 0.2 ~ 2MPa, and compress wind working pressure is 0.2 ~ 1MPa.
6. in accordance with the method for claim 1, it is characterized in that: oxidizing temperature is 200 ~ 240 DEG C, oxidization time is 2 ~ 10 hours.
7. in accordance with the method for claim 1, it is characterized in that: oxidizing reaction is carried out in a shear condition, shears rotating speed is 3000 ~ 6000rpm.
8. in accordance with the method for claim 1, it is characterized in that: the softening temperature of high softening point bitumen product is between 120 ~ 200 DEG C.
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| CN105586063B (en) * | 2014-10-22 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of preparation method of drilling fluid high softening point bitumen |
| CN106318424B (en) * | 2015-07-03 | 2019-04-12 | 宝武炭材料科技有限公司 | Novel environment-friendly method for improving asphalt softening point |
| CN110272764B (en) * | 2019-06-04 | 2020-12-29 | 新奥科技发展有限公司 | Preparation method of semicoke fly ash modifier and utilization method of semicoke fly ash |
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|---|---|---|---|---|
| GB229690A (en) * | 1924-02-22 | 1925-12-03 | Knud Waldemar Nielsen | Method of treating asphalt oil or pitch with a view to producing rubber-like masses therefrom |
| SU925981A1 (en) * | 1980-06-18 | 1982-05-07 | Украинский научно-исследовательский углехимический институт | Process for producing electrode pitch |
| CN1415699A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for oxidizing asphaltum |
| CN101688122A (en) * | 2006-06-08 | 2010-03-31 | 马拉松石油加拿大有限公司 | Bitum oxidation |
| CN101838542A (en) * | 2010-05-19 | 2010-09-22 | 镇江新光冶金辅材厂 | Manufacturing method of ultra-temperature pitch |
| CN102464989A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of high softening point asphalt |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120132565A1 (en) * | 2010-11-29 | 2012-05-31 | Exxonmobil Research And Engineering Company | Asphalt oxidation process using liquid jet ejection |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB229690A (en) * | 1924-02-22 | 1925-12-03 | Knud Waldemar Nielsen | Method of treating asphalt oil or pitch with a view to producing rubber-like masses therefrom |
| SU925981A1 (en) * | 1980-06-18 | 1982-05-07 | Украинский научно-исследовательский углехимический институт | Process for producing electrode pitch |
| CN1415699A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for oxidizing asphaltum |
| CN101688122A (en) * | 2006-06-08 | 2010-03-31 | 马拉松石油加拿大有限公司 | Bitum oxidation |
| CN101838542A (en) * | 2010-05-19 | 2010-09-22 | 镇江新光冶金辅材厂 | Manufacturing method of ultra-temperature pitch |
| CN102464989A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of high softening point asphalt |
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