CN101085828A - Method for preparing condensation polycyclic polynuclear aromatic hydrocarbon resin - Google Patents
Method for preparing condensation polycyclic polynuclear aromatic hydrocarbon resin Download PDFInfo
- Publication number
- CN101085828A CN101085828A CN 200710015699 CN200710015699A CN101085828A CN 101085828 A CN101085828 A CN 101085828A CN 200710015699 CN200710015699 CN 200710015699 CN 200710015699 A CN200710015699 A CN 200710015699A CN 101085828 A CN101085828 A CN 101085828A
- Authority
- CN
- China
- Prior art keywords
- temperature
- hydrocarbon resin
- aromatic hydrocarbon
- polycyclic
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Fats And Perfumes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention dislcoses a method for preparing condensed polycyclic and polynuclear aromatic hydrocarbon resin, belonging to chemical industry field. It takes polycyclic aromatics in dead oil or coal oil as raw material and employs process of polycyclic aromatics derivant preparation to prepare high thermal- resistant and high- strength condensed polycyclic and polynuclear aromatic hydrocarbon resin. It comprises following steps: enriching petroleum polycyclic aromatics component, carrying out reaction with enriched aromatics component with derivant under catalytic action, getting polycyclic aromatics, hydrolyzing polycyclic aromatics derivant or reacting with base for replacing, getting polycyclic aromatics fusel; polycondensing with polycyclic aromatics and getting final product. The invention is characterized by low cost and high performance product, and it provides a new way of polycyclic aromatics application with high added value.
Description
Technical field
The present invention relates to a kind of preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin, especially be raw material with the polycyclic aromatic hydrocarbons in oil or the coal tar, adopt the method for preparing the polycyclic aromatic hydrocarbons derivative, prepare the method for high heat resistance, high strength condensation polycyclic polynuclear aromatic hydrocarbon resin.
Background technology
Oil is non-renewable resource, faces exhausted danger, and the problem that how to make full use of existing petroleum resources development of new high added value chemical materials product also becomes increasingly conspicuous.Because the heaviness of crude oil is more and more serious, boiling point has accounted for the about 40% of crude oil total amount greater than 500 ℃ residual oil in the world wide, and is domestic even have and reach more than 50%.Annual China residual oil output can reach 6,000 ten thousand～7,000 ten thousand tons.But at present China's oil residual oil utilize approach very limited, mainly as road bitumen or building asphalt, or as oil fuel at a low price.The huge potential value that this has not only wasted petroleum residual oil does not meet the requirement of green economy development yet.Polycyclic aromatic hydrocarbons is one of topmost component in the petroleum residual oil, and polycyclic aromatic hydrocarbons has the cationoid reaction activity, can obtain the polynuclear aromatic hydrocarbons resin after polycondensation.That the polynuclear aromatic hydrocarbons resin has is high temperature resistant, corrosion-resistant, modulus is high, with multiple performances such as the macromolecule matrix consistency is good.The polynuclear aromatic hydrocarbons resin can match in excellence or beauty with polyimide, but cost will reduce greatly.In addition, the polynuclear aromatic hydrocarbons resin can show special electromagnetism behavior, may become novel organo-metallic material or low density organic magnetic macromolecular material, in electronic industry unique application will be arranged.With the polynuclear aromatic hydrocarbons resin is that the compound technology of disperse phase and speciality polymer material will be opened up the new way of utilizing the polynuclear aromatic hydrocarbons resource, can obtain the Multifucntional product, has broad application prospects.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin, especially be raw material with the polycyclic aromatic hydrocarbons in oil or the coal tar, adopt the method for preparing the polycyclic aromatic hydrocarbons derivative to prepare condensation polycyclic polynuclear aromatic hydrocarbon resin.
The present invention solves its technical problem and carries out as follows:
1. the enrichment of oil polycyclic aromatic hydrocarbons component.With the petroleum residual oil is raw material, and adopting furfural or pyrrolidone is that solvent carries out liquid-liquid extraction, obtains rich fragrant component and poor fragrant component.In temperature is 50 ℃～100 ℃, agent-oil ratio is that saturated part of content of rich fragrant component under 1: 1～3: 1 the situation is 8.00wt%～28.00wt%, aromaticity content is 72.00wt%～92.00wt%, saturated minute content of poor fragrant component is 52.00wt%～72.00wt%, and aromaticity content is 28.00wt%～48.00wt%.Come together and component and remove through shallow degree thermal polycondensation and distillation and obtain rich fragrant component after desolvating.
2. the aromatic component of enrichment and derivating agent react in the presence of catalyzer, obtain the polycyclic aromatic hydrocarbons derivative.Adopt bromine water (Br respectively
2) or concentrated hydrochloric acid (HCl) or the vitriol oil (H
2SO
4) or SO
3Be oxygenant, with FeCl
3Or AlO
3For catalyzer carries out prepared in reaction polycyclic aromatic hydrocarbons derivative, reaction conditions is respectively:
Rich fragrant component: the Br of oil
2(weight ratio)=(8～10): 1;
Temperature of reaction is 50～140 ℃; Reaction times 15min～120min; Or
Rich fragrant component: HCl (weight ratio)=(5～8) of oil: 1;
Temperature of reaction is 40～90 ℃; Reaction times 30min～180min; Or
Rich fragrant component: the H of oil
2SO
4(weight ratio)=(8～10): 1;
Temperature of reaction is 60～90 ℃; Reaction times 30min～60min.
Above-mentioned reacting middle catalyst content is the 1.00wt%～7.00wt% of total amount, and reaction product is the derivative of polycyclic aromatic hydrocarbons.
3. the polycyclic aromatic hydrocarbons derivative be hydrolyzed again the reaction or with alkali generation replacement(metathesis)reaction, obtain the polycyclic aromatic hydrocarbons fusel.Add sodium hydroxide or potassium hydroxide solution in the derivative of polycyclic aromatic hydrocarbons, temperature of reaction is 60～90 ℃; Reaction times 30min～120min; The reaction product washing is filtered, obtain semi-solid thickness product,, obtain the fragrant fusel of many cyclophanes 115 ℃ of following vacuum-dryings.
4. the polycyclic aromatic hydrocarbons fusel again with polycyclic aromatic hydrocarbons generation polycondensation, obtain polycyclic polynuclear aromatic hydrocarbon resin.Reaction conditions is: 120～180 ℃ of temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin at 1～3 hour time; 220～340 ℃ of temperature, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin at 5～10 hours time.
The present invention is a raw material with the polycyclic aromatic hydrocarbons in petroleum residual oil or the coal tar, adopt the method for preparing the polycyclic aromatic hydrocarbons derivative to prepare high heat resistance, high strength condensation polycyclic polynuclear aromatic hydrocarbon resin, started the basis of using the polycyclic aromatic hydrocarbons macromolecular material, obtain high performance macromolecular material with low cost raw material, for the high value added utilization of petroleum residual oil has been opened up new way.The present invention can reduce synthetic cost more than 60% compared with prior art, can improve the utilization ratio about 15% of raw material (petroleum residual oil or coal tar), has remarkable advantages and unusual effect technically.
Embodiment
Below in conjunction with embodiment in detail the present invention is described in detail.All operations process in following examples all is a normal pressure except that other has indicating.
Embodiment 1
With the FCC slurry oil is raw material, is that solvent carries out the liquid-liquid extraction arene rich with the furfural.Aromatic component accounts for 62.80wt% in the FCC slurry oil, in the saturated 37.20wt% that is divided into, 50 ℃ of temperature, agent-oil ratio be 1: 1 time through the extraction after obtain rich fragrant component and poor fragrant component, aromaticity content reaches 90.50wt% in the wherein rich fragrant component, the saturated 9.50wt% that is divided into.Aromaticity content is 37.20wt% in poor fragrant component, the saturated 72.80wt% that is divided into.Adopting rich aromatic component is the preparation that raw material carries out derivative.Get rich aromatic component: Br
2=8: 1 (weight ratio) adds FeCl
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is up to 120 ℃, and the reaction times is 2 hours, obtains the aromatic hydrocarbons brominated derivative, and productive rate is 31.00wt%.The concentration that adds 3 times of weight in the aromatic hydrocarbons brominated derivative is that 50% NaOH solution obtained many ring fusels in 1 hour 70 ℃ of following isothermal reactions, and yield is 76.40wt%.Many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, react 2.5 hours down for 165 ℃ in temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 8 hours down for 240 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.Thermotolerance through thermogravimetric analysis (TGA) C rank polycyclic polynuclear aromatic hydrocarbon resin is better, beginning weightless temperature (T
0) be 210 ℃, 10.00wt% weightless temperature (T
1) be 390 ℃, center weightless temperature (T
2) (the pairing temperature of half of maximum weight loss) be 455 ℃, 400 ℃ of weightlessness (W
400) be 6.00wt%, 800 ℃ of sample percent weight loss (W
800) be 40.00wt%.
Embodiment 2
The FCC slurry oil is that solvent carries out the liquid-liquid extraction arene rich with the pyrrolidone.Aromatic component accounts for 55.20wt% in the FCC slurry oil, in the saturated 45.80wt% that is divided into, 50 ℃ of temperature, agent-oil ratio 1: 1 time obtains rich fragrant component and poor fragrant component after extraction, aromaticity content reaches 76.80wt% in the wherein rich fragrant component, the saturated 23.20wt% that is divided into.Aromaticity content is 28.80wt% in poor fragrant component, the saturated 71.20wt% that is divided into.Adopting rich aromatic component is the preparation that raw material carries out derivative.Get rich aromatic component: HCl=5: 1 (weight ratio) adds Al
2O
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is up to 90 ℃, and the reaction times is 3 hours, obtains the aromatic hydrocarbons chlorinated derivatives, and productive rate is 31.00wt%.The concentration that adds 3 times of weight in the aromatic hydrocarbons chlorinated derivatives is that 40% KOH solution obtained many ring fusels in 1.5 hours 65 ℃ of following isothermal reactions, and yield is 67.33wt%.Many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, 170 ℃ of temperature, react 1.5 hours, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 7 hours down for 230 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.Through thermogravimetric analysis (TGA), C rank polycyclic polynuclear aromatic hydrocarbon resin begins weightless temperature (T
0) be 225 ℃, 10.00wt% weightless temperature (T
1) be 378 ℃, center weightless temperature (T
2) be 481 ℃, 400 ℃ of weightlessness (W
400) be 12.00wt%, 800 ℃ of percent weight loss (W
800) be 38.00wt%.
Embodiment 3
With the FCC slurry oil is raw material, is that solvent carries out the liquid-liquid extraction arene rich with the furfural.Aromatic component accounts for 62.80wt% in the FCC slurry oil, in the saturated 37.20wt% that is divided into, 50 ℃ of temperature, agent-oil ratio be 1: 1 time through the extraction after obtain rich fragrant component and poor fragrant component, aromaticity content reaches 90.50wt% in the wherein rich fragrant component, the saturated 9.50wt% that is divided into.Aromaticity content is 37.20wt% in poor fragrant component, the saturated 72.80wt% that is divided into.Adopting rich aromatic component is the preparation that raw material carries out derivative.Get rich aromatic component: H
2SO
4=8: 1 (weight ratio) adds FeCl
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is 60 ℃, and the reaction times is 1 hour, obtains the aromatic hydrocarbons sulfonated derivative, and productive rate is 32.00wt%.The concentration that adds 3 times of weight in the aromatic hydrocarbons sulfonated derivative is 50% NaOH solution, obtains many ring fusels in 1 hour 70 ℃ of following isothermal reactions, and yield is 72.30wt%.Many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, react 2.5 hours down for 160 ℃ in temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 5 hours down for 230 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.Thermotolerance through thermogravimetric analysis (TGA) C rank polycyclic polynuclear aromatic hydrocarbon resin is better, beginning weightless temperature (T
0) be 205 ℃, 10.00wt% weightless temperature (T
1) be 375 ℃, center weightless temperature (T
2) (the pairing temperature of half of maximum weight loss) be 452 ℃, 400 ℃ of weightlessness (W
400) be 16.00wt%, 800 ℃ of sample percent weight loss (W
800) be 48.00wt%.
Embodiment 4
The FCC slurry oil is that solvent carries out the liquid-liquid extraction arene rich with the pyrrolidone.Aromatic component accounts for 55.20wt% in the FCC slurry oil, in the saturated 45.80wt% that is divided into, 50 ℃ of temperature, agent-oil ratio 1: 1 time obtains rich fragrant component and poor fragrant component after extraction, aromaticity content reaches 76.80wt% in the wherein rich fragrant component, the saturated 23.20wt% that is divided into.Aromaticity content is 28.80wt% in poor fragrant component, the saturated 71.20wt% that is divided into.Adopting rich aromatic component is the preparation that raw material carries out derivative.Get rich aromatic component: H
2SO
4=9: 1 (weight ratio) adds Al
2O
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is up to 90 ℃, and the reaction times is 1 hour, obtains the aromatic hydrocarbons sulfonated derivative, and productive rate is 32.00wt%.The concentration that adds 3 times of weight in the aromatic hydrocarbons sulfonated derivative is 40% KOH solution, obtains many ring fusels in 1.0 hours 65 ℃ of following isothermal reactions, and yield is 62.43wt%.Many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, 180 ℃ of temperature, react 1 hour, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 5 hours down for 220 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.Through thermogravimetric analysis (TGA), C rank polycyclic polynuclear aromatic hydrocarbon resin begins weightless temperature (T
0) be 235 ℃, 10.00wt% weightless temperature (T
1) be 388 ℃, center weightless temperature (T
2) be 481 ℃, 400 ℃ of weightlessness (W
400) be 12.00wt%, 800 ℃ of percent weight loss (W
800) be 42.00wt%.
Embodiment 5
The FCC slurry oil is that solvent carries out the liquid-liquid extraction arene rich with the pyrrolidone.Aromatic component accounts for 55.20wt% in the FCC slurry oil, in the saturated 45.80wt% that is divided into, 70 ℃ of temperature, agent-oil ratio 2: 1 times obtains rich fragrant component and poor fragrant component after extraction, aromaticity content reaches 72.60wt% in the wherein rich fragrant component, the saturated 27.30wt% that is divided into.Aromaticity content is 32.40wt% in poor fragrant component, the saturated 67.50wt% that is divided into.Adopting rich aromatic component is the preparation that raw material carries out derivative.Get rich aromatic component: H
2SO
4=9: 1 (weight ratio) adds Al
2O
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is up to 90 ℃, and the reaction times is 1 hour, obtains the aromatic hydrocarbons sulfonated derivative, and productive rate is 29.00wt%.The concentration that adds 3 times of weight in the aromatic hydrocarbons sulfonated derivative is 40% KOH solution, obtains many ring fusels in 1.0 hours 65 ℃ of following isothermal reactions, and yield is 55.45wt%.Many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, react 1 hour down for 180 ℃ in temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 5 hours down for 220 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.Through thermogravimetric analysis (TGA), C rank polycyclic polynuclear aromatic hydrocarbon resin begins weightless temperature (T
0) be 234 ℃, 10.00wt% weightless temperature (T
1) be 385 ℃, center weightless temperature (T
2) be 477 ℃, 400 ℃ of weightlessness (W
400) be 15.00wt%, 800 ℃ of percent weight loss (W
800) be 48.00wt%.
Embodiment 6
Petroleum residual oil is that solvent carries out liquid-liquid extraction with propane, 100 ℃ of temperature, agent-oil ratio 3: 1, pressure 42MPa down deasphalted oil.Aromaticity content is 64.66% in the deasphalted oil, saturatedly is divided into 35.34%.It is 83.60wt% that deasphalted oil obtains rich fragrant component concentration through the furfural solvent extraction, saturated minute 16.40wt%.Aromatic hydrocarbons 36.90wt% in the poor fragrant component, saturated minute 63.10wt%.Get rich fragrant component: Br
2=8: 1 (weight ratio) adds FeCl
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is 120 ℃, and constant temperature time is 2 hours, obtains the aromatic hydrocarbons brominated derivative, and productive rate is 33.00wt%.The concentration that adds 3 times of weight in the aromatic hydrocarbons brominated derivative is 40% KOH solution, obtains many ring fusels in 1.5 hours 65 ℃ of following isothermal reactions, and yield is 69.12wt%.Many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, react 1.5 hours down for 170 ℃ in temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin, and productive rate is 85.10wt%, 103 ℃ of softening temperatures.Got C rank polycyclic polynuclear aromatic hydrocarbon resin in 9 hours at 300 ℃ of following constant temperature again, the sclerosis yield is 63.8wt%, and through thermogravimetric analysis (TGA), its thermotolerance index is T
0=210 ℃, T
1=392 ℃, T
2=415 ℃, W
400=17.00wt%,, W
800=49.00wt%.
Embodiment 7
Petroleum residual oil is that solvent carries out liquid-liquid extraction with propane, is 100 ℃ in temperature, agent-oil ratio 3: 1, extract under the pressure 42MPa deasphalted oil.Aromaticity content is 64.66% in the deasphalted oil, saturatedly is divided into 35.34%.It is 83.60wt% that deasphalted oil obtains rich fragrant component concentration through the furfural solvent extraction, saturated minute 16.40wt%.Aromatic hydrocarbons 36.90wt% in the poor fragrant component, saturated minute 63.10wt%.Get rich fragrant component: H
2SO
4=10: 1 (weight ratio) adds FeCl
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is 90 ℃, and the time is 1 hour, obtains the aromatic hydrocarbons sulfonated derivative, and productive rate is 31.00wt%.The concentration that adds 3 times of weight in the aromatic hydrocarbons sulfonated derivative is 40% KOH solution, obtains many ring fusels in 1.0 hours 65 ℃ of following isothermal reactions, and yield is 63.15wt%.Many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, react 1.0 hours down for 160 ℃ in temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin, and productive rate is 82.70wt%, 108 ℃ of softening temperatures.Got C rank polycyclic polynuclear aromatic hydrocarbon resin in 10 hours at 220 ℃ of following constant temperature again, the sclerosis yield is 64.8wt%, and through thermogravimetic analysis (TGA) (TGA), its thermotolerance index is T
0=220 ℃, T
1=389 ℃, T
2=413 ℃, W
400=17.00wt%, W
800=52.00wt%.
And at present thermotolerance preferably the thermal weight loss index of polyimide be: T
0=210 ℃, T
1=395 ℃, T
2=470 ℃, W
400=15.00wt%, W
800Thermotolerance when=50.00wt%, the C rank polycyclic polynuclear aromatic hydrocarbon resin high temperature of visible the foregoing description gained is better than polyimide.
The condensation polycyclic polynuclear aromatic resins can be used as the aspects such as resin base material, oil-free lubricatoin material and high temperature adhesive of carbon/carbon and carbon/plastic composite materials as novel hot setting resin, also can be used as the excellent presoma of materials such as charcoal fiber, graphite monocrystalline, diamond thin, compound between graphite layers.Especially with its outstanding high temperature resistance, lubricity, the opering characteristic of electric apparatus with fabulous affinity of carbon material etc. and be with a wide range of applications.The present invention provides new approach for the utilization of residual oil.
Claims (8)
1. the preparation method of a condensation polycyclic polynuclear aromatic hydrocarbon resin is characterized in that with the polycyclic aromatic hydrocarbons in oil or the coal tar be raw material, carries out as follows:
(1) enrichment of oil polycyclic aromatic hydrocarbons component: with the petroleum residual oil is raw material, adopting furfural or pyrrolidone is solvent, in temperature is 50 ℃～100 ℃, agent-oil ratio is respectively under 1: 1～3: 1 the situation and carries out liquid-liquid extraction, come together component through distillation remove desolvate and shallow degree thermal polycondensation after obtain rich fragrant component;
(2) aromatic component of enrichment and derivating agent react in the presence of catalyzer, obtain the polycyclic aromatic hydrocarbons derivative: adopt bromine water (Br respectively
2) or concentrated hydrochloric acid (HCl) or the vitriol oil (H
2SO
4) or SO
3Be oxygenant, with FeCl
3Or AlO
3For catalyzer carries out prepared in reaction polycyclic aromatic hydrocarbons derivative, reaction conditions is respectively:
Rich fragrant component: the Br of oil
2(weight ratio)=(8～10): 1;
Temperature of reaction is 50～140 ℃; Reaction times 15min～120min; Or
Rich fragrant component: HCl (weight ratio)=(5～8) of oil: 1;
Temperature of reaction is 40～90 ℃; Reaction times 30min～180min; Or
Rich fragrant component: the H of oil
2SO
4(weight ratio)=(8～10): 1;
Temperature of reaction is 60～90 ℃; Reaction times 30min～60min,
Above-mentioned reacting middle catalyst content is 1.00%～7.00wt% of total amount, and reaction product is the derivative of polycyclic aromatic hydrocarbons;
(3) the polycyclic aromatic hydrocarbons derivative of gained be hydrolyzed again reaction or with alkali generation replacement(metathesis)reaction, obtain the polycyclic aromatic hydrocarbons fusel: add sodium hydroxide or potassium hydroxide solution in the derivative of polycyclic aromatic hydrocarbons, temperature of reaction is 60～90 ℃; Reaction times 30min～120min; The reaction product washing is filtered, obtain semi-solid thickness product,, obtain the fragrant fusel of many cyclophanes 115 ℃ of following vacuum-dryings;
(4) the polycyclic aromatic hydrocarbons fusel again with polycyclic aromatic hydrocarbons generation polycondensation, obtain polycyclic polynuclear aromatic hydrocarbon resin: reaction conditions is 120～180 ℃ of temperature, 1～3 hour time, obtains thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Under 220～340 ℃ of temperature, in 5～10 hours reaction times, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin again.
2. the preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin according to claim 1 is characterized in that with the FCC slurry oil be raw material, with the furfural be solvent 50 ℃ of temperature, agent-oil ratio is to carry out the liquid-liquid extraction arene rich 1: 1 time, rich aromatic component: the Br of gained
2=8: 1 (weight ratio) adds FeCl
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, temperature of reaction is up to 140 ℃, reaction times is 2 hours, obtains the aromatic hydrocarbons brominated derivative, and the concentration that adds 3 times of weight again in the aromatic hydrocarbons brominated derivative is 50% NaOH solution, obtained many ring fusels in 1 hour 70 ℃ of following isothermal reactions, many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, react 2.5 hours down for 165 ℃ in temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 8 hours down for 240 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.
3. the preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin according to claim 1 is characterized in that with the FCC slurry oil be raw material, is solvent with the pyrrolidone, 50 ℃ of temperature, agent-oil ratio carries out the liquid-liquid extraction arene rich 1: 1 time, and rich aromatic component: the HCl=5 of gained: 1 (weight ratio) adds Al
2O
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, temperature of reaction is up to 90 ℃, and the reaction times is 3 hours, obtains the aromatic hydrocarbons chlorinated derivatives, the concentration that adds 3 times of weight again in the aromatic hydrocarbons chlorinated derivatives is 40% KOH solution, obtained many ring fusels in 1.5 hours 65 ℃ of following isothermal reactions, encircle fusel more and synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, under 170 ℃ of temperature, reacted 1.5 hours, and obtained thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 7 hours down for 230 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.
4. the preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin according to claim 1, it is characterized in that the FCC slurry oil is that solvent carries out the liquid-liquid extraction arene rich with the pyrrolidone, 50 ℃ of temperature, agent-oil ratio carries out the liquid-liquid extraction arene rich 1: 1 time, rich aromatic component: the H of gained
2SO
4=8: 1 (weight ratio) adds FeCl
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is 60 ℃, and the reaction times is 1 hour, obtains the aromatic hydrocarbons sulfonated derivative; The concentration that adds 3 times of weight in the aromatic hydrocarbons sulfonated derivative is 50% NaOH solution, obtains many ring fusels in 1 hour 70 ℃ of following isothermal reactions; Many ring fusels reacted 2.5 hours down for 120 ℃ in temperature with the fragrant component of richness again, obtained thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; 230 ℃ of temperature, reacted 5 hours, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.
5. the preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin according to claim 1 is characterized in that the FCC slurry oil is that solvent carries out the liquid-liquid extraction arene rich with the pyrrolidone, and 50 ℃ of temperature, agent-oil ratio extracts at 1: 1, rich aromatic component: the H of gained
2SO
4=9: 1 (weight ratio) adds Al
2O
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is up to 90 ℃, and the reaction times is 1 hour, obtains the aromatic hydrocarbons sulfonated derivative; The concentration that adds 3 times of weight in the aromatic hydrocarbons sulfonated derivative is 40% KOH solution, obtained many ring fusels in 1.0 hours 65 ℃ of following isothermal reactions, many ring fusels reacted 1 hour down for 180 ℃ in temperature with the fragrant component of richness again, obtained thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 5 hours down for 220 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.
6. the preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin according to claim 1, it is characterized in that the FCC slurry oil with the pyrrolidone be solvent 70 ℃ of temperature, agent-oil ratio carries out the liquid-liquid extraction arene rich 2: 1 times, rich aromatic component: the H of gained
2SO
4=9: 1 (weight ratio) adds Al
2O
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, and temperature of reaction is up to 90 ℃, reaction times is 1 hour, obtain the aromatic hydrocarbons sulfonated derivative, the concentration that adds 3 times of weight in the aromatic hydrocarbons sulfonated derivative is 40% KOH solution, obtains many ring fusels in 1.0 hours 65 ℃ of following isothermal reactions; Many ring fusels reacted 1 hour down for 180 ℃ in temperature with the fragrant component of richness again, obtained thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Reacted 5 hours down for 220 ℃ in temperature again, obtain insoluble infusible C rank polycyclic polynuclear aromatic hydrocarbon resin.
7. the preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin according to claim 1, it is characterized in that with the petroleum residual oil being raw material, with propane is that solvent is 100 ℃ of temperature, agent-oil ratio 3: 1, pressure is to carry out liquid-liquid extraction under the 42MPa to get deasphalted oil, deasphalted oil obtains rich fragrant component through the furfural solvent extraction, rich fragrant component: the Br of gained
2=8: 1 (weight ratio) adds FeCl
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, temperature of reaction is 120 ℃, constant temperature time is 2 hours, obtains the aromatic hydrocarbons brominated derivative, and the concentration that adds 3 times of weight again in the aromatic hydrocarbons brominated derivative is 40% KOH solution, obtained many ring fusels in 1.5 hours 65 ℃ of following isothermal reactions, many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, react 1.5 hours down for 170 ℃ in temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin; Got C rank polycyclic polynuclear aromatic hydrocarbon resin in 9 hours 300 ℃ of following isothermal reactions again.
8. the preparation method of condensation polycyclic polynuclear aromatic hydrocarbon resin according to claim 1, it is characterized in that petroleum residual oil is that solvent is 100 ℃ of temperature with propane, agent-oil ratio 3: 1, carry out liquid-liquid extraction under the pressure 42MPa and get deasphalted oil, deasphalted oil obtains rich fragrant component and poor fragrant component through the furfural solvent extraction, rich fragrant component: the H of gained
2SO
4=10: 1 (weight ratio) adds FeCl
3Make catalyzer, its dosage accounts for the 5.00wt% of total amount, temperature of reaction is 90 ℃, constant temperature time is 1 hour, obtain the aromatic hydrocarbons sulfonated derivative, the concentration that adds 3 times of weight in the aromatic hydrocarbons sulfonated derivative is 40% KOH solution, obtained many ring fusels in 1.0 hours 65 ℃ of following isothermal reactions, many ring fusels synthesize polycyclic polynuclear aromatic hydrocarbon resin with the fragrant component reaction of richness again, reacted 1.0 hours down for 160 ℃ in temperature, obtain thermoset B rank polycyclic polynuclear aromatic hydrocarbon resin, got C rank polycyclic polynuclear aromatic hydrocarbon resin in 10 hours through 220 ℃ of following constant temperature again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710015699 CN101085828A (en) | 2007-06-06 | 2007-06-06 | Method for preparing condensation polycyclic polynuclear aromatic hydrocarbon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710015699 CN101085828A (en) | 2007-06-06 | 2007-06-06 | Method for preparing condensation polycyclic polynuclear aromatic hydrocarbon resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101085828A true CN101085828A (en) | 2007-12-12 |
Family
ID=38937015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710015699 Pending CN101085828A (en) | 2007-06-06 | 2007-06-06 | Method for preparing condensation polycyclic polynuclear aromatic hydrocarbon resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101085828A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298546B (en) * | 2008-07-01 | 2011-12-28 | 东营华业新材料有限公司 | Method for producing electrical brush adhesive by far infrared heating |
| CN102453227A (en) * | 2010-10-26 | 2012-05-16 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
| CN101838409B (en) * | 2009-03-18 | 2013-06-12 | 中国石油大学(北京) | Residual oil fire retardant composition and fire retardant polyolefin composite material and method for preparing same |
-
2007
- 2007-06-06 CN CN 200710015699 patent/CN101085828A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298546B (en) * | 2008-07-01 | 2011-12-28 | 东营华业新材料有限公司 | Method for producing electrical brush adhesive by far infrared heating |
| CN101838409B (en) * | 2009-03-18 | 2013-06-12 | 中国石油大学(北京) | Residual oil fire retardant composition and fire retardant polyolefin composite material and method for preparing same |
| CN102453227A (en) * | 2010-10-26 | 2012-05-16 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
| CN102453227B (en) * | 2010-10-26 | 2013-05-22 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Research status, industrial application demand and prospects of phenolic resin | |
| CN102173980B (en) | Method for preparing phenolic chemicals through thermo-chemical conversion of industrial lignin | |
| CN103242881B (en) | The method of separate bitumen class material from coal directly-liquefied residue | |
| CN109609111B (en) | Wood tar resin sand consolidation agent and preparation method and application thereof | |
| CN102718934B (en) | Cashew nut shell oil modified resorcinol bonding resin and preparation method thereof | |
| CN107189802A (en) | A kind of method that FCC slurry hydro-upgrading segmentation thermal polycondensation prepares mesophase pitch | |
| CN102786979B (en) | Process for preparing needle coke raw material by using medium and low temperature coal tar and high temperature pitch | |
| Li et al. | Microwave‐assisted hydrothermal liquefaction of lignin for the preparation of phenolic formaldehyde adhesive | |
| CN102399563A (en) | Method for preparing general type coal series asphalt with spinnability by solvent extraction and oxidative thermopolymerization | |
| CN101230199B (en) | Method for preparing asphalt-based nano composite material | |
| CN101906317A (en) | Method for preparing environment-friendly aromatic oil from catalytic cracking slurry oil | |
| CN105838409A (en) | Method for preparing mesophase pitch from residues of coal liquefaction and prepared mesophase pitch | |
| CN102408740A (en) | Molding compound modified by organosolv lignin or derivative thereof and preparation method thereof | |
| CN101085828A (en) | Method for preparing condensation polycyclic polynuclear aromatic hydrocarbon resin | |
| CN103755926B (en) | Condensation multinuclear polyaromatic hydrocarbon resin and preparation method thereof | |
| CN101781575A (en) | Method for preparing high-cleanness fuel oil from intermediate-temperature and low-temperature coal tar | |
| CN1141358C (en) | Method for preparing heat-resisting pitch resin by using heavy residuum as raw material | |
| CN103756703A (en) | Modified asphalt, method for preparing modified asphalt by using direct liquefied coal residue in normal pressure continuous mode and application of modified coal residue | |
| CN102875752B (en) | Lignin modified thermoplastic phenolic resin and preparation method thereof | |
| CN103319672A (en) | Tear resistant phenolic resin and preparation method thereof | |
| CN102786984B (en) | Process for preparing needle coke raw material by using medium and low temperature coal tar | |
| CN103232605A (en) | Hydrogenated phenolic pyrolysis lignin and preparation method thereof | |
| Li et al. | Catalytic hydrolysis of cellulose to total reducing sugars with superior recyclable magnetic multifunctional MCMB‐based solid acid as a catalyst | |
| CN107384462A (en) | A kind of two sections of FCC slurry faces the method that hydrogen modification thermal polycondensation prepares mesophase pitch | |
| CN107652331A (en) | A kind of lignin depolymerization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20071212 |