Background technology
" intermittently temperature and the modified pitch production technique in the single kettle type " of Chinese patent: ZL200410033280.2, the production technique of once finishing middle temperature and modified pitch in a kind of single still is disclosed, it is long to have solved the mid-temperature pitch production cycle, modified pitch needs the state of the art of multi-still continuous production, and whole technological process only needs 28-36 hour.Processing method mainly is: the coal tar raw material processed is to water content≤5%, coal-fired hot waste gas is heated, fire box temperature is 800-900 ℃, negative pressure, i.e. distillation tower vacuum tightness 0.04-0.075Pa in the still, heat to steam and slip, after cutting out mixed triolein and carbolineum, residue makes the mid-temperature pitch product through cooling process: continue the upgrading of heating, make the mid-temperature pitch upgrading make transformation of the way pitch, through cooling process, be the modified pitch product.This technical matters is simple, is easy to operate and control, and less investment, small scale is particularly suitable for the small-scale production enterprise implement and adopts.
" a kind of modifying asphalt and production method thereof " number of patent application of Anshan University of Science and Technology's application is: 03133782.1, patent publication No. is: CN1570026, its production method mainly is with the volatilizable composition of γ resin, converts the β resin to as far as possible, reduces α resin content in the pitch.The modifying asphalt characteristics are that the bitumen flue gas quantity discharged has reduced more than 50% when being heated to 400 ℃, and have the thermosetting characteristic.The modifying asphalt of producing with present method has linearity molecular structure; 10 ℃~180 ℃ of softening temperatures; β resin content 10~50%; The α resin content increases ≯ 1.0% before the modification on year-on-year basis.The production stage of modifying asphalt is: material choice; Meticulous distillation; Add polymkeric substance; Adjust the pH value; Condensation reaction; Neutralization reaction; Vacuum exhaust, release discharge.The modifying asphalt that present method is produced has linearity molecular structure; 10~180 ℃ of softening temperatures; β resin content 10~50%; The α resin content increases ≯ 1.0% before the modification on year-on-year basis, can be widely used in the binding agent of greying carbon element electrode; Prebaked anode, cathode carbon pieces wedding agent; Pave the way, the building operation waterproof; Replace carbon containing refractory and comprise magnesia typing or unsetting product wedding agent resin etc., and effect is better than existing various asphaltic products.es.
" from the method for coal tar production chemical product and oil fuel " of Chinese patent: ZL 200410012455.1, a kind of method of producing chemicals and oil fuel from coal tar is disclosed, it becomes coal tar fractional distillation light, weighs two fractions, and light fraction is lightweight coal tar and tar-bitumen.Light fraction is produced light-end products through hydrofining or upgrading.The combination of the processing of tar-bitumen and pit kiln or with the delayed coking combination, not only production more chemical products phenol, naphthalene and gasoline, diesel oil or light Fuel etc. also can improve the quality or the direct production high carbon coke of pit kiln coke.Add a kind of inhibitor simultaneously, suppress slow down in the boiler tube or reactor in the knot charcoal, ensuring equipment can long-term operation.
The high molecular-weight average of bituminous makes it to be difficult to further cut into different components, have only by solvent and just can make it to be separated into different components, and components contents and ratio in the pitch directly influence bituminous softening temperature, viscosity, plasticity, rheological and charing performance.More than disclosed technology, all can not form bituminous effectively and separate, thus can not produce softening temperature at 275~285 ℃ high softening point bitumen, QI less than 0.1% the pitch and the pitch of other special purposes.High softening point bitumen is widely used in charcoal fiber, globular graphite, nuclear graphite etc., and purifying pitch is mainly used in the production needle coke.
Summary of the invention
A kind of complete processing that is prepared multiple pitch and oil fuel by coal tar of providing at the deficiencies in the prior art is provided, it has solved in the coal-tar pitch processing can not produce high softening point bitumen and low quinoline insolubles bituminous a great problem, improved the added value of coal tar processing greatly, it is few to have facility investment, easy to operate, pollute little, the measured characteristics of bituminous matter.
The object of the present invention is achieved like this: a kind ofly prepare the working method of multiple pitch and oil fuel by coal tar, it may further comprise the steps:
1, atmospheric distillation
Enter the atmospheric distillation tower after feed coal tar is heated to 350~360 ℃, 220~250 ℃ of mixed fraction that cat head cuts are sale of finished goods after condensation, and the viscid bitumen cut send next procedure to handle at the bottom of the tower.
2, rectification under vacuum
Above-mentioned viscid bitumen cut and solvent oil all merged be heated to the rectifying of 360 ℃ of laggard rectification under vacuum towers, 190~200 ℃ of light constituents that cat head cuts are combined as solvent oil and viscid bitumen after condensation, 200~205 ℃ of light constituents that tower top side line cuts deallocation system operation after condensation is produced oil fuel, and softening pitch then send next procedure to handle at the bottom of the tower.
3, one-level super from
Above-mentioned softening pitch is carried out super separation, and the softening pitch after the separation send secondary super from operation, and its impurity is provided and delivered and made operation production oil fuel.
4, secondary super from
With one-level super from after pitch by purposes carry out secondary super from, prepare purifying pitch, impregnating pitch, modified pitch and high softening point bitumen respectively.
Described high softening point bitumen be with secondary super from after part pitch send into oxidizing tower, 220~360 ℃ of tower temperature, 12~16 hours time, divide three oxidations, remove the impurity aftershaping through vaporizer, strainer then and form.
Described modified pitch be with secondary super from after part pitch and the part pitch after the oxidation form through the upgrading that is combined.
Described impregnating pitch be with secondary super from after part pitch send into reactor, 80~120 ℃ of still temperature, dip treating formed in 3~4 hours.
Described oil fuel be the top extraction of rectification under vacuum tower light constituent through after the condensation with one-level super from after impurity through preparing mixed forming.
Described solvent oil is combined by 8~12% (weight ratios) and viscid bitumen.
Technology of the present invention is simple, easy to operate, it can produce multiple high-quality pitch and oil fuel, it is few to have facility investment, stay-in-grade characteristics, thus it is low to have solved the whole grade of the present pitch of China better, the problem that coal-tar pitch cut instability and impurity are many, improve the added value and the bituminous quality of coal tar processing, be fit to very much the processing of coal tar.
Embodiment
Consult Fig. 1, the present invention is undertaken by following processing step:
Embodiment one:
1, atmospheric distillation
With 50kg coal tar, be heated to 350 ℃ and enter the atmospheric distillation tower, after total reflux for some time, after all stablizing Deng the parameters of tower, begin to excise 230 ℃ of mixed fraction cuts of cat head, sell with industrial chemicals from the mixed fraction of side line anthracene oil section extraction 45%, tower bottom distillates 55% viscid bitumen cut.
2, rectification under vacuum
In atmospheric distillation tower bottom distilled viscid bitumen cut, add the 5kg solvent oil, solvent oil is the mixed solvent based on NMP (pyrrolidone), ℃ enter vacuum still rectifying with viscid bitumen uniform mixing post-heating to 360,195 ℃ of light constituents that cat head cuts after condensation as the be mixed solvent oil of usefulness of viscid bitumen, produce oil fuel from 200 ℃ of light constituents deallocation system operation after condensation that tower top side line cuts, the softening pitch of the overhead product at the bottom of the tower send the super operation of one-level to handle.
3, one-level super from
Above-mentioned softening pitch is sent into ultracentrifuge separate, the pitch after the separation send that secondary is super to be handled from operation, one-level super from after impurity and be mixed through the light constituent cut of the vacuum still top extraction of condensation and make finished product oil fuel.
4, secondary super from
With one-level super from after pitch by purposes carry out secondary super from, the bitumen production modified pitch of the super respectively bitumen production impregnating pitch from the purifying pitch that goes out 15kg, 3kg, 2kg, the bitumen production oxidized bitumen of 2kg are for producing modified pitch and high softening point bitumen.
5, oxidized bitumen
With secondary super from after 2kg pitch send into oxidizing tower, divide three oxidations, oxidizing temperature is 230 ℃ for the first time, and oxidization time is 4 hours, and oxidizing temperature is 310 ℃ for the second time, oxidization time is 4 hours, oxidizing temperature is 340 ℃ for the third time, and oxidization time is 8 hours, removes impurity by vaporizer, strainer after three oxide treatment of oxidizing tower, partial oxidation pitch makes high softening point bitumen after moulding, partial oxidation pitch is for producing modified pitch.
6, modified pitch
With secondary super from after 2kg pitch after the processing of uniform mixing upgrading, make modified pitch with partial oxidation pitch.
7, impregnating pitch
With secondary super from after 3kg pitch send into reactor, 100 ℃ of still temperature, dip treating made impregnating pitch after 3 hours.
Table 1 is the technical feature of modified pitch in the GB8730-88 standard
Table 1
The modified pitch technical feature that table 2 is produced for the present invention
Index |
Parameter |
Softening temperature (ring)/℃ |
113℃ |
Toluene insolubles |
|
(extraction process)/% |
20% |
Quinoline insolubles/% |
12% |
β resin/% |
19% |
Coking value/% |
58% |
Ash content/% |
0.1% |
Table 2
The high softening point bitumen index that the present invention produces:
Softening temperature: 282 ℃, TI:78%, QI:23%
The impregnating pitch index that the present invention produces:
Softening temperature: 86 ℃, TI:24%, QI:0.1%
Embodiment two:
1, atmospheric distillation
With 100kg coal tar, be heated to 355 ℃ and enter the atmospheric distillation tower, after total reflux for some time, after all stablizing Deng the parameters of tower, begin to excise 240 ℃ of mixed fraction cuts of cat head, sell with industrial chemicals from the mixed fraction of side line anthracene oil section extraction 45%, tower bottom distillates 55% viscid bitumen cut.
2, rectification under vacuum
In atmospheric distillation tower bottom distilled viscid bitumen cut, add the 12kg solvent oil, solvent oil is the mixed solvent based on NMP (pyrrolidone), ℃ enter vacuum still with viscid bitumen uniform mixing post-heating to 360,200 ℃ of light constituents that cat head cuts after condensation as the be mixed solvent oil of usefulness of viscid bitumen, produce oil fuel from 202 ℃ of light constituents deallocation system operation after condensation that tower top side line cuts, the softening pitch of the overhead product at the bottom of the tower send the super operation of one-level to handle.
3, one-level super from
Above-mentioned softening pitch is sent into ultracentrifuge separate, the pitch after the separation send that secondary is super to be handled from operation, one-level super from after impurity and be mixed through the light constituent cut of the vacuum still top extraction of condensation and make finished product oil fuel.
4, secondary super from
With one-level super from after pitch by purposes carry out secondary super from, the bitumen production modified pitch of the super respectively bitumen production impregnating pitch from the purifying pitch that goes out 30kg, 6kg, 4kg, the bitumen production oxidized bitumen of 4kg are for producing modified pitch and high softening point bitumen.
5, oxidized bitumen
With secondary super from after 4kg pitch send into oxidizing tower, divide three oxidations, oxidizing temperature is 240 ℃ for the first time, and oxidization time is 3 hours, and oxidizing temperature is 310 ℃ for the second time, oxidization time is 3 hours, oxidizing temperature is 350 ℃ for the third time, and oxidization time is 7 hours, removes impurity by vaporizer, strainer after three oxide treatment of oxidizing tower, partial oxidation pitch makes high softening point bitumen after moulding, partial oxidation pitch is for producing modified pitch.
6, modified pitch
With secondary super from after 4kg pitch after the processing of uniform mixing upgrading, make modified pitch with partial oxidation pitch.
7, impregnating pitch
With secondary super from after 6kg pitch send into reactor, 90 ℃ of still temperature, dip treating made impregnating pitch after 3.5 hours.
Table 3 is the technical feature of the modified pitch of the embodiment of the invention two productions
Index |
Parameter |
Softening temperature (ring)/℃ |
112℃ |
Toluene insolubles |
|
(extraction process)/% |
19% |
Quinoline insolubles/% |
13% |
β resin/% |
18% |
Coking value/% |
56% |
Ash content/% |
0.1% |
Table 3
The high softening point bitumen index that the embodiment of the invention two is produced:
Softening temperature: 284 ℃, TI:76%, QI:22%
The impregnating pitch index that the embodiment of the invention two is produced:
Softening temperature: 85 ℃, TI:23%, QI:0.1%.