A method for high-value utilization of phenol tar by catalytic cracking

Abstract

The present invention relates to the field of petrochemical technology, in particular to a method for high-value utilization of phenol tar catalytic cracking, wherein cumylphenol and α-methylstyrene dimer (AMSD) in phenol tar are cracked into phenol and α-methylstyrene (α-MS) under the action of a catalyst by adding a catalyst, and are evaporated together with light components such as acetophenone; by adding a trace amount of polymerization inhibitor, secondary polymerization of phenol and α-MS during the reaction is avoided, and the yield of cracking products reaches more than 30%; by adding high-temperature solvent oil, the pour point of cracking residues can be significantly reduced. The catalytic cracking residues can be used as fuel, and can also be used as a raw material for fixed bed residual oil hydrogenation or heavy oil slurry bed hydrogenation.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical industry, and in particular to a method for high-value utilization of phenol tar by catalytic cracking. Background Art

[0002] Phenol tar is a byproduct of the cumene process for the preparation of phenol and acetone and is a hazardous waste. In 2023, the annual output of phenol tar in my country will be close to 300,000 tons, accounting for about 5-10% of the finished phenol.

[0003] Phenol, acetophenone and α-methylstyrene in phenol tar are all important organic chemical raw materials. Phenol can be directly returned to the phenol device for use. Acetophenone has a wide range of uses. It can be used as a synthetic raw material for medicines, spices, pesticides, dyes, etc. It can also be used as a solvent for cellulose, resins, etc. It is also used as an extractant in industry. At present, the extraction of acetophenone from phenol tar has become an important source of acetophenone internationally. α-Methylstyrene can also be used as the main monomer for the manufacture of synthetic resins and plastics, and can also be directly hydrogenated to produce isopropylbenzene, which can be directly returned to the device for use.

[0004] The traditional treatment measure for phenol tar is hot furnace co-combustion, but because it contains a large amount of α-methylstyrene and phenol, it can polymerize and coke at a relatively low temperature, causing pipeline blockage, equipment corrosion and other problems. In the process of treatment, wastewater, waste gas, waste residue and other secondary environmental problems will also be generated, such as the emission of PAHs, NOx, SOx, etc. Therefore, exploring the effective utilization of chemical tars including phenol tar has always been a research hotspot for the resource disposal of hazardous wastes such as distillation residues. If the useful components in phenol tar (such as phenol, acetophenone and α-methylstyrene) can be recovered, and α-methylstyrene dimer and cumylphenol can be cracked into phenol and α-methylstyrene with higher value, it will not only improve the economic benefits of the phenol device, but also reduce the amount of hazardous waste generated, which has both economic and environmental significance.

[0005] The main methods for obtaining useful substances from phenol tar include thermal decomposition and catalytic cracking. (1) The thermal decomposition method is simple to operate, but has problems such as low reaction efficiency, high reaction temperature, and low recovery rate. (2) The catalytic cracking method is to add a catalyst to phenol tar to crack AMSD and cumylphenol in the phenol tar into α-MS and phenol, which are recovered together with acetophenone and the like. Compared with the thermal decomposition method, the catalytic cracking method can significantly reduce the reaction temperature and shorten the reaction time, and can obtain a higher yield of light components.

[0006] Chinese patent (CN1154399A) discloses a method for recovering valuable products from phenol tar, wherein 0.1wt-0.2wt% phosphoric acid is added to the phenol tar as a catalyst, and the reaction is carried out in a column reactor at a reaction temperature of 200-360° C. The added phosphoric acid is dehydrated and polymerized to form polyphosphoric acid. Although the phosphoric acid added in this method can catalyze the cracking of cumylphenol and AMSD, since the catalyst is easy to volatilize and decompose, a large amount of AMSD and cumylphenol exist in the product due to the secondary polymerization of α-MS and phenol.

[0007] A Chinese invention patent (CN117865781) discloses a method and system for cracking and recovering phenol tar. The method preheats phenol tar with an organic silver salt catalyst and then performs a cracking reaction to obtain a light component and a heavy component. The organic silver salt catalyst is selected from one or more of silver palmitate, silver stearate, silver caprate, and silver dilaurate. The method has problems such as low cracking yield and high catalyst cost. Summary of the invention

[0008] The purpose of the present invention is to provide a method for high-value utilization of phenol tar by catalytic cracking, so as to solve the technical problems in the background technology.

[0009] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is:

[0010] A method for high-value utilization of phenol tar by catalytic cracking, which mainly comprises the following steps:

[0011] Step 1: adding measured phenol tar, and then adding the catalyst into the cracking kettle;

[0012] Step 2: Add high temperature resistant diluent oil and inhibitor while adding the catalyst;

[0013] Step 3: gradually raising the temperature to 200-340°C to crack cumylphenol and AMSD into phenol and α-MS, which are then distilled off together with the light component of acetophenone, and the product is recovered after being cooled in a condenser;

[0014] Step 4: Wait until there is no distillate at the distillation outlet and the reaction is finished.

[0015] Furthermore, the catalyst is one or more of organic acid, inorganic acid, acidic ionic liquid, strong acid and weak base salt, solid acid, solid base and acidic oxide or alkaline substance, preferably inorganic acid and acidic oxide.

[0016] Furthermore, the catalyst is added in an amount of 0.05%-5%, preferably 0.1%-2%.

[0017] Furthermore, the cracking reaction temperature range is 200-340°C, preferably 240-300°C, and particularly preferably 300°C.

[0018] Furthermore, the high temperature resistant diluent oil is one or more of industrial white oil, heat transfer oil, heavy diesel oil, and liquid paraffin, preferably industrial white oil or liquid paraffin with a boiling point greater than 300°C.

[0019] Furthermore, the amount of the high temperature resistant diluent oil added is 5%-40%, preferably 10%-20%.

[0020] Furthermore, the polymerization inhibitor is one of 2-sec-butyl-4,6-dinitrophenol (DNBP) or 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one (QM-Ph), preferably DNBP.

[0021] Furthermore, the addition amount of the polymerization inhibitor is 5-500 ppm, preferably 30-300 ppm.

[0022] As an improvement, the beneficial effects of the present invention are:

[0023] The invention provides a method for high-value utilization of phenol tar by catalytic cracking, which cracks cumylphenol and AMSD in the phenol tar into phenol and α-MS, and recovers acetophenone while recovering phenol and α-MS, thereby realizing high-value utilization of phenol tar. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a data comparison table of a method for high-value utilization of phenol tar by catalytic cracking according to the present invention; DETAILED DESCRIPTION

[0025] In order to make the contents of the present invention more clearly understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0026] This embodiment provides a method for high-value utilization of phenol tar by catalytic cracking, which mainly includes the following steps:

[0027] Step 1: adding measured phenol tar, and then adding the catalyst into the cracking kettle;

[0028] Step 2: Add high temperature resistant diluent oil and inhibitor while adding the catalyst;

[0029] Step 3: gradually raising the temperature to 200-340°C to crack cumylphenol and AMSD into phenol and α-MS, which are then distilled off together with the light component of acetophenone, and the product is recovered after being cooled in a condenser;

[0030] Step 4: Wait until there is no distillate at the distillation outlet and the reaction is finished.

[0031] In this embodiment, the catalyst is one or more of an organic acid, an inorganic acid, an acidic ionic liquid, a strong acid and a weak base salt, a solid acid, a solid base, an acidic oxide or an alkaline substance, preferably an inorganic acid and an acidic oxide.

[0032] In this embodiment, the amount of catalyst added is 0.05%-5%, preferably 0.1%-2%.

[0033] In this embodiment, the cracking reaction temperature range is 200-340°C, preferably 240-300°C, and particularly preferably 300°C.

[0034] In this embodiment, the high temperature resistant diluent oil is one or more of industrial white oil, heat transfer oil, heavy diesel oil, and liquid paraffin, preferably industrial white oil or liquid paraffin with a boiling point greater than 300°C.

[0035] In this embodiment, the amount of high temperature resistant diluent oil added is 5%-40%, preferably 10%-20%.

[0036] In this embodiment, the polymerization inhibitor is one of 2-sec-butyl-4,6-dinitrophenol (DNBP) or 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one (QM-Ph), preferably DNBP.

[0037] In this embodiment, the amount of the polymerization inhibitor added is 5-500 ppm, preferably 30-300 ppm.

[0038] Embodiment 1:

[0039] 1000g of phenol tar is added into a cracking kettle, and 1% of ammonium phosphate is added, and 20% of high temperature resistant diluent oil and 100ppm of inhibitor are added at the same time, and the temperature is gradually raised to 280°C to crack cumylphenol and AMSD into phenol and α-MS, which are evaporated together with light components such as acetophenone, and the product is recovered after being cooled in a condenser; the reaction is terminated when there is no distillate at the distillation outlet.

[0040] Comparative Example 1: 1000 g of phenol tar was added to a cracking kettle, 20% of a high temperature resistant diluent oil and 100 ppm of an inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were then distilled off together with light components such as acetophenone. The product was cooled in a condenser and recovered; the reaction was terminated when there was no distillate at the distillation outlet.

[0041] Comparative Example 2: 1000 g of phenol tar was added to a cracking kettle, 0.2% ammonium phosphate, 20% high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were evaporated together with light components such as acetophenone, and the product was recovered after cooling in a condenser; the reaction was terminated when there was no distillate at the distillation outlet.

[0042] Comparative Example 3: 1000 g of phenol tar was added to a cracking kettle, 0.2% ammonium sulfate, 20% high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were then distilled off together with light components such as acetophenone. The product was cooled in a condenser and recovered; the reaction was terminated when there was no distillate at the distillation outlet.

[0043] Comparative Example 4: 1000 g of phenol tar was added to a cracking kettle, 2% ammonium phosphate, 20% high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were then distilled off together with light components such as acetophenone, and the product was recovered after being cooled in a condenser; the reaction was terminated when there was no distillate at the distillation outlet.

[0044] Comparative Example 5: 1000 g of phenol tar was added to a cracking kettle, 2% molybdenum disulfide, 20% high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were then distilled off together with light components such as acetophenone, and the product was recovered after being cooled in a condenser; the reaction was terminated when there was no distillate at the distillation outlet.

[0045] Comparative Example 6: 1000 g of phenol tar was added to a cracking kettle, 2% Y-type molecular sieve, 20% high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were then distilled off together with light components such as acetophenone, and the product was recovered after being cooled in a condenser; the reaction was terminated when there was no distillate at the distillation outlet.

[0046] Comparative Example 7: 1000 g of phenol tar was added to a cracking kettle, 2% calcium oxide, 20% high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were then distilled off together with light components such as acetophenone. The product was cooled in a condenser and recovered; the reaction was terminated when there was no distillate at the distillation outlet.

[0047] Comparative Example 8: 1000 g of phenol tar was added to a cracking kettle, 2% sodium hydroxide, 20% high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were then distilled off together with light components such as acetophenone, and the product was recovered after being cooled in a condenser; the reaction was terminated when there was no distillate at the distillation outlet.

[0048] Comparative Example 9: 1000 g of phenol tar was added to a cracking kettle, 1% of ionic liquid 1, 20% of high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were evaporated together with light components such as acetophenone, and the product was recovered after cooling in a condenser; the reaction was terminated when there was no distillate at the distillation outlet.

[0049] Comparative Example 10: 1000 g of phenol tar was added to a cracking kettle, 1% Y ionic liquid 2, 20% high temperature resistant diluent oil and 100 ppm of inhibitor were added, and the temperature was gradually raised to 280° C. to crack cumylphenol and AMSD into phenol and α-MS, which were evaporated together with light components such as acetophenone, and the product was recovered after cooling in a condenser; the reaction was terminated when there was no distillate at the distillation outlet.

[0050] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for high-value utilization of phenol tar by catalytic cracking, which mainly comprises the following steps: Step 1: adding measured phenol tar, and then adding the catalyst into the cracking kettle; Step 2: Add high temperature resistant diluent oil and inhibitor while adding the catalyst; Step 3: gradually raising the temperature to 200-340°C to crack cumylphenol and AMSD into phenol and α-MS, which are then distilled off together with the light component of acetophenone, and the product is recovered after being cooled in a condenser; Step 4: Wait until there is no distillate at the distillation outlet and the reaction is finished.

2. A method for high-value utilization of phenol tar by catalytic cracking according to claim 1, characterized in that: The catalyst is one or more of organic acid, inorganic acid, acidic ionic liquid, strong acid and weak base salt, solid acid, solid base and acidic oxide or alkaline substance, preferably inorganic acid and acidic oxide.

3. A method for high-value utilization of phenol tar by catalytic cracking according to claim 2, characterized in that: The added amount of the catalyst is 0.05%-5%, preferably 0.1%-2%.

4. A method for high-value utilization of phenol tar by catalytic cracking according to claim 1, characterized in that: The cracking reaction temperature range is 200-340°C, preferably 240-300°C, and particularly preferably 300°C.

5. A method for high-value utilization of phenol tar by catalytic cracking according to claim 1, characterized in that: The high temperature resistant diluent oil is one or more of industrial white oil, heat transfer oil, heavy diesel oil, and liquid paraffin, preferably industrial white oil or liquid paraffin with a boiling point greater than 300°C.

6. A method for high-value utilization of phenol tar by catalytic cracking according to any one of claims 1 or 5, characterized in that: The addition amount of the high temperature resistant diluent oil is 5%-40%, preferably 10%-20%.

7. A method for high-value utilization of phenol tar by catalytic cracking according to claim 1, characterized in that: The polymerization inhibitor is one of 2-sec-butyl-4,6-dinitrophenol (DNBP) or 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one (QM-Ph), preferably DNBP.

8. A method for high-value utilization of phenol tar by catalytic cracking according to any one of claims 1 or 7, characterized in that: The addition amount of the polymerization inhibitor is 5-500 ppm, preferably 30-300 ppm.

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