Development process for improving chromaticity of high-boiling-point aromatic hydrocarbon

Abstract

The invention discloses a development process for improving chromaticity of high-boiling-point aromatic hydrocarbon, and aims to solve the problems that in the prior art, the color of the aromatic hydrocarbon is not good enough, the aromatic hydrocarbon is easy to generate crystalline components at low temperature, the viscosity at low temperature is too high, the aromatic hydrocarbon is easy to oxidize, the storage performance is poor, the quality is unstable, and the process needs to introduce hydrogen, so that the cost is low. And economic benefits are not high. The development process comprises the following steps: step 1, weighing raw materials, then putting the raw materials into a reaction tank, starting to stir, heating the raw materials, and after the raw materials reach a reaction temperature, weighing an initiator with the required weight, and carrying out free radical polymerization reaction; according to the development process, the carclazyte is added, alkali nitrogen and colloid in the solvent oil are adsorbed, the ultrasonic generator is matched, the reaction effect is improved, the reaction time is shortened, and therefore the chromaticity of the aromatic hydrocarbon is improved, the obtained aromatic hydrocarbon is not prone to oxidation and more stable in quality, hydrogen does not need to be introduced in the preparation process, and economic benefits are higher.

Description

Technical Field

[0001] The invention belongs to the technical field of aromatic hydrocarbons, and particularly relates to a development process for improving the chroma of high-boiling-point aromatic hydrocarbons. Background Art

[0002] High-boiling-point aromatic hydrocarbon series solvents are produced using reformed aromatic hydrocarbons as raw materials. They have the characteristics of strong dissolving power, low toxicity, low odor, low sulfur content, high boiling point, slow volatility, and are free of water, olefins, chlorine, and heavy metals. They also have stable chemical and physical properties and good leveling properties. Due to their good solubility, they can be used as cleaning agents for precision machinery and as emulsifiers for preparing pesticides. They are also widely used in high-end inks.

[0003] At present, the invention patent with patent number CN201410438551.6 discloses a method for producing high-boiling-point aromatic solvent oil. C10 aromatic hydrocarbons are used as raw materials, catalytically hydrogenated, and distilled and separated to obtain the fraction with a temperature of 150-180°C or the fraction with a temperature of 180-215°C, which is the high-boiling-point aromatic solvent oil. Among them, the hydrogenation catalyst adopts an amorphous silica-aluminum composite carrier, and the loaded active ingredient oxides are nickel oxide, molybdenum oxide, tungsten oxide and phosphorus oxide; the total weight of the active ingredient oxides is 20% to 60% of the weight of the silica-aluminum composite carrier, preferably 30% to 55%; the weight ratio of nickel oxide, molybdenum oxide, tungsten oxide and phosphorus oxide is 10 to 30:50 to 85:3 to 20:0.5 to 8, preferably 12 to 20:65 to 85:3 to 10:0.5 to 5; the weight ratio of silica to alumina in the amorphous silica-aluminum composite carrier is 20 to 70:30 to 80, preferably 50 to 70:30 to 50. The distillation kettle liquid with a boiling point above 215°C is returned to the hydrogenation reactor as raw material for recycling. The route design is reasonable and the utilization rate of C10 aromatic hydrocarbon resources is improved. However, the aromatic hydrocarbons produced by this process are not good enough in color, and the aromatic hydrocarbons are prone to produce crystalline components at low temperatures. The viscosity at low temperatures is too high and it is easily oxidized. The storage performance is poor and the quality is unstable. In addition, the process also requires the introduction of hydrogen, and the economic benefits are not high.

[0004] Therefore, the above-mentioned problems of poor color and excessive viscosity at low temperatures need to be solved urgently to improve the use scenarios of aromatics. Summary of the Invention

[0005] (1) Technical problems to be solved

[0006] In view of the shortcomings of the prior art, the present invention aims to provide a development process for improving the chroma of high-boiling-point aromatic hydrocarbons. The development process aims to solve the technical problems of the prior art, namely, that the color of aromatic hydrocarbons is not good enough, aromatic hydrocarbons easily produce crystallized components at low temperatures, the viscosity is too high at low temperatures, and they are easily oxidized, the storage performance is poor, the quality is unstable, and the process also requires the introduction of hydrogen, resulting in low economic benefits.

[0007] (2) Technical solution

[0008] In order to solve the above technical problems, the present invention provides a development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons, which comprises the following steps: Step 1: weighing the raw materials, then placing the raw materials into a reaction tank, starting stirring, and heating the raw materials. After the raw materials reach the reaction temperature, weighing the required weight of an initiator, and adding the initiator into the reaction tank in three portions. The initiator is decomposed by heat to generate free radicals, and a free radical polymerization reaction is carried out;

[0009] Step 2: Weigh the required amount of aluminum chloride, then dissolve the aluminum chloride in anhydrous ether to prepare a catalyst solution for later use;

[0010] Step 3: Then, the catalyst solution in step 2 is added dropwise to the reaction tank to carry out a catalytic polymerization reaction, and then methanol is added after cooling to 50° C., and then a solid base is added to terminate the catalytic polymerization reaction to obtain a polymer solution;

[0011] Step 4: removing aluminum chloride from the polymerization liquid, then filtering the polymerization liquid. The filtered polymerization liquid enters the distillation system, is heated to the primary distillation temperature, and the fraction in the range of 60-160°C is separated as methanol and ethanol solvents. It is then further heated to the secondary distillation temperature, and the fraction below 210°C is separated as aromatic solvent oil.

[0012] Step 5: Adding aromatic solvent oil to a reaction tank, adding a decolorant and toluene-methyl ethyl ketone, introducing nitrogen, stirring the aromatic solvent oil, decolorant and toluene-methyl ethyl ketone, heating to a refining temperature and maintaining the temperature, while turning on an ultrasonic generator, and the vibrator emits ultrasonic waves to the reaction tank to accelerate the reaction of toluene-methyl ethyl ketone, decolorant and aromatic solvent oil. After the refining is completed, cooling to room temperature to obtain a mixed solution;

[0013] Step 6: Add the mixed liquid to a centrifuge to remove the decolorizer and obtain high-boiling-point aromatic hydrocarbons.

[0014] Preferably, the raw material is a C9 fraction.

[0015] Preferably, the interval time for adding the initiator in step 1 is not less than 10 minutes, and the total amount of the initiator is 0.01% by weight of the raw materials.

[0016] Preferably, in step 1, the reaction temperature is 55-65° C., and the free radical polymerization reaction time is 1-1.5 h.

[0017] Preferably, the decolorizing agent is white clay, and the amount of the decolorizing agent used is 1%-5% by weight of the raw material.

[0018] Preferably, the catalytic polymerization reaction time in step 3 is 3-3.5 hours.

[0019] Preferably, the amount of aluminum chloride used is 1.5% by weight of the raw material.

[0020] Preferably, in step 4, the temperature of the first fraction is 148-152°C, and the temperature of the second fraction is 218-222°C.

[0021] Preferably, in step 5, the refining temperature is 45-50° C. and the holding time is 20-40 min.

[0022] Preferably, the ultrasonic frequency of the ultrasonic generator is 20-40 KHz.

[0023] (3) Beneficial effects

[0024] Compared with the prior art, the present invention has the following beneficial effects: the aromatic hydrocarbons produced by the developed process of the present invention have the characteristics of strong solvency, low toxicity, low odor, high boiling point, slow volatilization, no water and olefins, no chlorine and heavy metals, stable chemical and physical properties, and good leveling properties; toluene-methyl ethyl ketone is used to remove components of the aromatic hydrocarbons that crystallize at low temperatures, thereby solving the problem of excessive viscosity at low temperatures; the addition of white clay adsorbs alkaline nitrogen and colloid in the solvent oil; and the use of an ultrasonic generator improves the reaction effect and shortens the reaction time, thereby improving the chromaticity of the aromatic hydrocarbons; the obtained aromatic hydrocarbons are not easily oxidized and have more stable quality; hydrogen does not need to be introduced during the preparation process, and the economic benefits are higher. DETAILED DESCRIPTION

[0025] This specific embodiment is a development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons, and the steps are as follows: Step 1: weighing the weight of the raw materials, then placing the raw materials into a reaction tank, starting to stir, and heating the raw materials. After the raw materials reach the reaction temperature, weighing the required weight of the initiator, and adding the initiator into the reaction tank in three times, the initiator decomposes under heat to generate free radicals, and a free radical polymerization reaction is carried out;

[0026] Step 2: Weigh the required amount of aluminum chloride, then dissolve the aluminum chloride in anhydrous ether to prepare a catalyst solution for later use;

[0027] Step 3: Then, the catalyst solution in step 2 is added dropwise to the reaction tank to carry out a catalytic polymerization reaction, and then methanol is added after cooling to 50° C., and then a solid base is added to terminate the catalytic polymerization reaction to obtain a polymer solution;

[0028] Step 4: removing aluminum chloride from the polymerization liquid, then filtering the polymerization liquid. The filtered polymerization liquid enters the distillation system, is heated to the primary distillation temperature, and the fraction in the range of 60-160°C is separated as methanol and ethanol solvents. It is then further heated to the secondary distillation temperature, and the fraction below 210°C is separated as aromatic solvent oil.

[0029] Step 5: Adding aromatic solvent oil to a reaction tank, adding a decolorant and toluene-methyl ethyl ketone, introducing nitrogen, stirring the aromatic solvent oil, decolorant and toluene-methyl ethyl ketone, heating to a refining temperature and maintaining the temperature, while turning on an ultrasonic generator, and the vibrator emits ultrasonic waves to the reaction tank to accelerate the reaction of toluene-methyl ethyl ketone, decolorant and aromatic solvent oil. After the refining is completed, cooling to room temperature to obtain a mixed solution;

[0030] Step 6: Add the mixed liquid to a centrifuge to remove the decolorizer and obtain high-boiling-point aromatic hydrocarbons.

[0031] Example 1

[0032] When using the developed process of this technical solution to prepare high-boiling-point aromatics, the steps are as follows:

[0033] Step 1: Weigh the weight of the raw materials, and then put the raw materials into the reaction tank. The raw materials are C9 fractions. Stirring is started and the raw materials are heated. After the raw materials reach the reaction temperature of 55°C, the required weight of the initiator is weighed and added to the reaction tank in 3 times. The interval between adding the initiator is not less than 10 minutes, and the total amount of the initiator is 0.01% of the weight of the raw materials. The initiator decomposes when heated to generate free radicals, and a free radical polymerization reaction is carried out. The free radical polymerization reaction time is 1 hour;

[0034] Step 2: Weigh the required amount of aluminum chloride, the amount of which is 1.5% of the weight of the raw material, and then dissolve the aluminum chloride in anhydrous ether to prepare a catalyst solution for later use;

[0035] Step 3: Then, the catalyst solution in step 2 is added dropwise to the reaction tank to carry out a catalytic polymerization reaction for 3 hours. Then, methanol is added after cooling to 50° C., and then a solid base is added to terminate the catalytic polymerization reaction to obtain a polymer solution;

[0036] Step 4: removing aluminum chloride from the polymerization liquid, then filtering the polymerization liquid. The filtered polymerization liquid enters the distillation system, is heated to a primary fraction temperature of 152°C, and the fractions in the range of 60-160°C are separated as methanol and ethanol solvents. It is then further heated to a secondary fraction temperature of 222°C, and the fractions below 210°C are separated as aromatic solvent oil.

[0037] Step 5: adding aromatic solvent oil to a reaction tank, and adding a decolorant and toluene-methyl ethyl ketone, the decolorant is white clay, and the amount of the decolorant is 1% of the weight of the raw material, introducing nitrogen, stirring the aromatic solvent oil, decolorant and toluene-methyl ethyl ketone, heating to a refining temperature of 45°C and maintaining for 20 minutes, while turning on an ultrasonic generator with an ultrasonic frequency of 40KHz. The vibrator emits ultrasonic waves to the reaction tank to accelerate the reaction of toluene-methyl ethyl ketone, decolorant and aromatic solvent oil. After the refining is completed, cooling to room temperature to obtain a mixed solution;

[0038] Step 6: Add the mixed liquid to a centrifuge to remove the decolorizer and obtain high-boiling-point aromatic hydrocarbons.

[0039] The aromatic hydrocarbon prepared in this embodiment is a transparent liquid with a slightly turbid color and no odor. It is not easily oxidized by heat and the coating has good flatness.

[0040] Example 2

[0041] When using the developed process of this technical solution to prepare high-boiling-point aromatics, the steps are as follows:

[0042] Step 1: Weigh the weight of the raw materials, and then put the raw materials into the reaction tank. The raw materials are C9 fractions. Stirring is started and the raw materials are heated. After the raw materials reach the reaction temperature of 60°C, the required weight of the initiator is weighed and added to the reaction tank in three times. The interval between adding the initiator is not less than 10 minutes, and the total amount of the initiator is 0.01% of the weight of the raw materials. The initiator decomposes when heated to generate free radicals, and a free radical polymerization reaction is carried out. The free radical polymerization reaction time is 1.5 hours;

[0043] Step 2: Weigh the required amount of aluminum chloride, the amount of which is 1.5% of the weight of the raw material, and then dissolve the aluminum chloride in anhydrous ether to prepare a catalyst solution for later use;

[0044] Step 3: Then, the catalyst solution in step 2 is added dropwise to the reaction tank to carry out a catalytic polymerization reaction for 3 hours. Then, methanol is added after cooling to 50° C., and then a solid base is added to terminate the catalytic polymerization reaction to obtain a polymer solution;

[0045] Step 4: removing aluminum chloride from the polymerization liquid, then filtering the polymerization liquid. The filtered polymerization liquid enters the distillation system, is heated to a primary fraction temperature of 152°C, and the fractions in the range of 60-160°C are separated as methanol and ethanol solvents. It is then further heated to a secondary fraction temperature of 222°C, and the fractions below 210°C are separated as aromatic solvent oil.

[0046] Step 5: adding aromatic solvent oil to a reaction tank, and adding a decolorant and toluene-methyl ethyl ketone, the decolorant is white clay, and the amount of the decolorant is 3% of the weight of the raw material, introducing nitrogen, stirring the aromatic solvent oil, decolorant and toluene-methyl ethyl ketone, heating to a refining temperature of 45°C and maintaining for 30 minutes, while turning on an ultrasonic generator with an ultrasonic frequency of 40KHz. The vibrator emits ultrasonic waves to the reaction tank to accelerate the reaction of toluene-methyl ethyl ketone, decolorant and aromatic solvent oil. After the refining is completed, cooling to room temperature to obtain a mixed solution;

[0047] Step 6: Add the mixed liquid to a centrifuge to remove the decolorizer and obtain high-boiling-point aromatic hydrocarbons.

[0048] The aromatic hydrocarbon prepared in this embodiment is a transparent liquid with a relatively clear color and no odor. It is not easily oxidized by heat and the coating has good flatness.

[0049] Example 3

[0050] When using the developed process of this technical solution to prepare high-boiling-point aromatics, the steps are as follows:

[0051] Step 1: Weigh the weight of the raw materials, and then put the raw materials into the reaction tank. The raw materials are C9 fractions. Stirring and heating the raw materials are started. After the raw materials reach the reaction temperature of 60°C, weigh the required weight of the initiator and add the initiator to the reaction tank in 3 times. The interval between adding the initiator is not less than 10 minutes, and the total amount of the initiator is 0.01% of the weight of the raw materials. The initiator decomposes by heat to generate free radicals, and a free radical polymerization reaction is carried out. The free radical polymerization reaction time is 1 hour;

[0052] Step 2: Weigh the required amount of aluminum chloride, the amount of which is 1.5% of the weight of the raw material, and then dissolve the aluminum chloride in anhydrous ether to prepare a catalyst solution for later use;

[0053] Step 3: Then, the catalyst solution in step 2 is added dropwise to the reaction tank to carry out a catalytic polymerization reaction for 3.5 hours. Then, methanol is added after cooling to 50° C., and then a solid base is added to terminate the catalytic polymerization reaction to obtain a polymer solution;

[0054] Step 4: removing aluminum chloride from the polymerization liquid, then filtering the polymerization liquid. The filtered polymerization liquid enters the distillation system, is heated to a primary fraction temperature of 152°C, and the fractions in the range of 60-160°C are separated as methanol and ethanol solvents. It is then further heated to a secondary fraction temperature of 222°C, and the fractions below 210°C are separated as aromatic solvent oil.

[0055] Step 5: adding aromatic solvent oil to a reaction tank, and adding a decolorant and toluene-methyl ethyl ketone, the decolorant is white clay, and the amount of the decolorant is 4% of the weight of the raw material, introducing nitrogen, stirring the aromatic solvent oil, decolorant and toluene-methyl ethyl ketone, heating to a refining temperature of 50°C and maintaining for 30 minutes, while turning on an ultrasonic generator with an ultrasonic frequency of 40KHz. The vibrator emits ultrasonic waves to the reaction tank to accelerate the reaction of toluene-methyl ethyl ketone, decolorant and aromatic solvent oil. After the refining is completed, cooling to room temperature to obtain a mixed solution;

[0056] Step 6: Add the mixed liquid to a centrifuge to remove the decolorizer and obtain high-boiling-point aromatic hydrocarbons.

[0057] The aromatic hydrocarbon prepared in this embodiment is a transparent liquid with a very clear color and no odor. It is not easily oxidized by heat and the coating has good flatness.

[0058] Table 1 is the performance index of aromatic solvent oil

[0059]

[0060] Table 1.

Claims

1. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons, characterized in that: The steps are as follows: Step 1: Weigh the raw materials, then place them into a reaction tank, start stirring, and heat the raw materials. After the raw materials reach the reaction temperature, weigh the required weight of initiator and add the initiator into the reaction tank in three batches. The initiator decomposes under heat to generate free radicals, and a free radical polymerization reaction is carried out; Step 2: Weigh the required amount of aluminum chloride, then dissolve the aluminum chloride in anhydrous ether to prepare a catalyst solution for later use; Step 3: Then, the catalyst solution in step 2 is added dropwise to the reaction tank to carry out a catalytic polymerization reaction, and then methanol is added after cooling to 50° C., and then a solid base is added to terminate the catalytic polymerization reaction to obtain a polymer solution; Step 4: removing aluminum chloride from the polymerization liquid, then filtering the polymerization liquid. The filtered polymerization liquid enters the distillation system, is heated to the primary distillation temperature, and the fraction in the range of 60-160°C is separated as methanol and ethanol solvents. It is then further heated to the secondary distillation temperature, and the fraction below 210°C is separated as aromatic solvent oil. Step 5: Adding aromatic solvent oil to a reaction tank, adding a decolorant and toluene-methyl ethyl ketone, introducing nitrogen, stirring the aromatic solvent oil, decolorant and toluene-methyl ethyl ketone, heating to a refining temperature and maintaining the temperature, while turning on an ultrasonic generator, and the vibrator emits ultrasonic waves to the reaction tank to accelerate the reaction of toluene-methyl ethyl ketone, decolorant and aromatic solvent oil. After the refining is completed, cooling to room temperature to obtain a mixed solution; Step 6: Add the mixed liquid to a centrifuge to remove the decolorizer and obtain high-boiling-point aromatic hydrocarbons.

2. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: The raw material is C9 fraction.

3. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: The interval time for adding the initiator in the step 1 is not less than 10 minutes, and the total amount of the initiator is 0.01% by weight of the raw materials.

4. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: In the step 1, the reaction temperature is 55-65° C., and the free radical polymerization reaction time is 1-1.5 h.

5. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: The decolorizing agent is white clay, and the amount of the decolorizing agent is 1%-5% of the weight of the raw material.

6. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: The time of the catalytic polymerization reaction in step 3 is 3-3.5 hours.

7. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: The amount of aluminum chloride used is 1.5% by weight of the raw material.

8. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: In the step 4, the temperature of the first fraction is 148-152° C., and the temperature of the second fraction is 218-222° C.

9. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: In the step 5, the refining temperature is 45-50° C. and the holding time is 20-40 min.

10. A development process for improving the chromaticity of high-boiling-point aromatic hydrocarbons according to claim 1, characterized in that: The ultrasonic frequency of the ultrasonic generator is 20-40KHz.

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