Method for comprehensively utilizing phenolic ketone tar and petroleum fracturing propping agent

Abstract

The invention provides a method for comprehensively utilizing phenolic ketone tar and a petroleum fracturing proppant, and the method comprises the following steps: (1) mixing phenolic ketone tar and an acid catalyst to carry out a first heating reaction, and then adding an aldehyde compound to carry out a second heating reaction to obtain a phenolic resin mixture; (2) carrying out negative pressure rectification on the phenolic resin mixture to obtain a tower top material and a tower kettle material; wherein acetophenone is obtained after the tower top material is layered, and the tower kettle material comprises phenolic resin; (3) carrying out ring-opening reaction on the mixed phase transfer catalyst, epoxy chloropropane and phenolic resin, then adding alkali to carry out ring-closing reaction, and separating to obtain novolac epoxy resin; and (4) mixing the curing agent, the accelerant and the novolac epoxy resin for stirring reaction to obtain the petroleum fracturing propping agent. According to the method provided by the invention, acetophenone in the phenolic ketone tar can be separated out, the petroleum fracturing propping agent can be produced at the same time, the recovery energy consumption can be reduced, no solid waste is discharged, and the environmental protection requirement is met.

Description

Technical Field

[0001] The invention belongs to the technical field of petrochemical industry, and relates to a method for comprehensive utilization of phenol-ketone tar, in particular to a method for comprehensive utilization of phenol-ketone tar and a petroleum fracturing proppant. Background Art

[0002] Phenol is a key raw material for the production of chemicals such as resins, fungicides, preservatives, and pharmaceuticals. The cumene process is the most commonly used method for producing phenol, accounting for over 92% of global production. After separating the phenol and acetone products, cumene production equipment produces a large amount of tar discharged from the system. This tar, known as phenol-ketone tar, primarily consists of phenol, acetophenone, α-methylstyrene dimer, and cumylphenol.

[0003] Currently, the most commonly used method for disposing of phenol-ketone tar is to incinerate the by-product steam. This method has limited benefits and is prone to causing serious environmental problems. Therefore, green and efficient disposal processes are currently a research hotspot. Some studies have proposed extracting high-value components such as phenol and acetophenone from phenol-ketone tar. For example, CN113511959A discloses a system for separating phenol and acetophenone from tar. The phenol-ketone tar is de-weighted by a de-weighting tower, and the de-weighting tower kettle is heavy tar, which needs to be further incinerated. The overhead material of the de-weighting tower is passed through a coarse fractionation tower, a phenol distillation tower, and an acetophenone distillation tower to obtain phenol and acetophenone. Because phenol and acetophenone are azeotropic compounds, multiple cycles of pressure swing distillation are required to ensure the yield of pure products, resulting in high energy consumption. At the same time, the total content of phenol and acetophenone in phenol-ketone tar is generally less than 30%, and most of the tar still needs to be incinerated, which has little effect on improving environmental problems.

[0004] Other studies have proposed high-temperature cracking of phenol-ketone tar and recovery of α-methylstyrene. For example, CN116272713A discloses an apparatus and method for cracking phenol-ketone tar to recover α-methylstyrene. The phenol-ketone tar is continuously cracked at a temperature above 320°C and then subjected to negative pressure distillation to recover α-methylstyrene. This process has a high reaction temperature, and the raw materials and products are prone to forming heavy components with larger molecular weights. In addition, acetophenone cannot be recovered, resulting in a low yield of the target product. The process is economical and unsafe, making it difficult to apply in practice.

[0005] Furthermore, during oil and gas extraction, petroleum fracturing proppants enter the formation along with the high-pressure solution and fill the cracks in the rock formation, preventing the cracks from closing due to stress release. This helps maintain high conductivity, allowing oil and gas to flow smoothly and increasing production. Traditional petroleum fracturing proppants primarily consist of natural quartz sand and ceramsite. Quartz sand is widely available and inexpensive, but it has low compressive strength and cannot meet the requirements of high-pressure deep-well operations. Ceramsite proppants have high compressive strength and good conductivity, but they are dense and difficult to transport, resulting in high production costs. In recent years, resin-based fracturing proppants have been used in oil and gas extraction due to their high strength, low density, and chemical inertness. However, the high price of the raw material epoxy resin leads to high costs for fracturing proppants, which to some extent limits their widespread application.

[0006] It can be seen that how to provide a method for comprehensive utilization of phenol-ketone tar, simultaneously produce petroleum fracturing proppants, reduce recovery energy consumption, achieve zero solid waste emissions, and meet environmental protection requirements has become a problem that technical personnel in this field urgently need to solve. Summary of the Invention

[0007] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a method for the comprehensive utilization of phenol-ketone tar and a petroleum fracturing proppant. The method can separate acetophenone from phenol-ketone tar and produce petroleum fracturing proppant at the same time, which can reduce recovery energy consumption, achieve zero solid waste emission, and meet environmental protection requirements.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a method for comprehensive utilization of phenol-ketone tar, the method comprising at least the following steps:

[0010] (1) mixing phenol-ketone tar and an acidic catalyst to carry out a first temperature-raising reaction, and then adding an aldehyde compound to carry out a second temperature-raising reaction to obtain a phenolic resin mixture;

[0011] (2) subjecting the phenolic resin mixture obtained in step (1) to negative pressure distillation to obtain a tower top material and a tower bottom material; wherein the tower top material is separated into layers to obtain acetophenone, and the tower bottom material comprises a phenolic resin;

[0012] (3) mixing a phase transfer catalyst, epichlorohydrin and the phenolic resin obtained in step (2) to carry out a ring-opening reaction, then adding a base to carry out a ring-closing reaction, and separating to obtain a phenolic epoxy resin;

[0013] (4) mixing the curing agent, the accelerator and the phenolic epoxy resin obtained in step (3) and stirring the mixture to obtain an oil fracturing proppant.

[0014] The phenol-ketone tar contains at least phenol, acetophenone, α-methylstyrene dimer and cumylphenol.

[0015] The present invention first uses an acidic catalyst to decompose α-methylstyrene dimer in phenol-ketone tar into monomers, which are then condensed with phenol to generate cumylphenol. Then, an aldehyde compound is added to react with phenol and cumylphenol to generate phenolic resin. After the phenol is consumed, the azeotropic composition of phenol and acetophenone is broken, thereby significantly reducing the difficulty of purifying acetophenone. After the acetophenone is extracted, the remaining tar is synthesized into phenolic epoxy resin, and then into a petroleum fracturing proppant.

[0016] Compared with conventional phenol-ketone tar resource utilization methods, the acetophenone separation process of the present invention is simple and has low energy consumption. After further resource utilization, there is basically no solid waste emission, and the final product has high added value. It is a green, safe and economically beneficial phenol-ketone tar resource utilization method.

[0017] In addition, the present invention uses industrial waste such as phenol-ketone tar as a raw material for preparing petroleum fracturing proppants, which greatly reduces the use cost of petroleum fracturing proppants and achieves a significant reduction or zero emission of phenol-ketone tar during the comprehensive utilization process. Cumylphenol is further condensed with phenolic aldehyde to produce phenolic epoxy resin. Due to the presence of branched groups, the comprehensive performance of the obtained petroleum fracturing proppant is effectively improved.

[0018] Preferably, the phenol-ketone tar is the heavy component tar produced by the cumene process to produce phenol and acetone.

[0019] Preferably, the acidic catalyst in step (1) comprises any one of sulfuric acid, hydrochloric acid, benzenesulfonic acid or toluenesulfonic acid, or a combination of at least two thereof.

[0020] Preferably, the amount of the acidic catalyst added in step (1) is 0.5%-10% of the mass of the phenol-ketone tar.

[0021] Preferably, the target temperature of the first temperature-raising reaction in step (1) is 60° C.-120° C., and the reaction time is 1 h-6 h.

[0022] Preferably, the aldehyde compound in step (1) comprises formaldehyde aqueous solution and / or paraformaldehyde.

[0023] Preferably, the concentration of the formaldehyde aqueous solution is 30%-40%.

[0024] Preferably, the amount of the aldehyde compound added in step (1) is 1%-100% of the mass of the phenol-ketone tar.

[0025] Preferably, the target temperature of the second temperature-raising reaction in step (1) is 80° C.-130° C., and the reaction time is 2 h-8 h.

[0026] Preferably, the number of theoretical plates of the negative pressure distillation in step (2) is 5-50.

[0027] Preferably, the operating pressure of the negative pressure distillation in step (2) is 1 kPa-60 kPa.

[0028] Preferably, the reflux ratio of the negative pressure distillation in step (2) is 0.1-5.

[0029] Preferably, the phase transfer catalyst in step (3) comprises benzyltriethylammonium chloride.

[0030] Preferably, the mixing mass ratio of the phase transfer catalyst, epichlorohydrin and phenolic resin in step (3) is (0.01-0.02):(5-6):1.

[0031] Preferably, the alkali in step (3) comprises a sodium hydroxide solution with a concentration of 45%-50%.

[0032] Preferably, the amount of base added in step (3) is 40%-50% of the mass of the phenolic resin.

[0033] Preferably, the curing agent in step (4) includes any one or a combination of at least two of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 4,4'-diaminodiphenylmethane, m-phenylenediamine, m-phenylenediamine or 4,4'-diaminodiphenyl sulfone.

[0034] Preferably, the accelerator in step (4) comprises any one or a combination of at least two of 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, phenol, o-cresol or resorcinol.

[0035] Preferably, the mixing mass ratio of the curing agent, accelerator and phenolic epoxy resin in step (4) is (0.1-1):(0.01-0.1):1.

[0036] Preferably, the stirring reaction in step (4) is carried out in a dispersant.

[0037] Preferably, the dispersant comprises silicone oil and / or dimethyl silicone oil.

[0038] Preferably, the mixing mass ratio of the dispersant to the phenolic epoxy resin is (30-60):1.

[0039] Preferably, the stirring reaction in step (4) is carried out at a temperature of 120° C. to 180° C. and for a time of 10 min to 300 min.

[0040] Preferably, the phenol-ketone tar is subjected to a weight removal treatment and / or phenol is added before comprehensive utilization.

[0041] In a second aspect, the present invention provides a petroleum fracturing proppant prepared by the method for comprehensive utilization of phenol-ketone tar as described in the first aspect, wherein the petroleum fracturing proppant has a glass transition temperature of 155°C-190°C.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] (1) The present invention first uses an acidic catalyst to decompose α-methylstyrene dimer in phenol-ketone tar into monomers, which are then condensed with phenol to form cumylphenol. Then, an aldehyde compound is added to react with phenol and cumylphenol to form a phenolic resin. After the phenol is consumed, the azeotropic composition of phenol and acetophenone is broken, thereby significantly reducing the difficulty of purifying acetophenone. After the acetophenone is extracted, the remaining tar is synthesized into a phenolic epoxy resin, and then a petroleum fracturing proppant is synthesized.

[0044] (2) Compared with conventional phenol-ketone tar resource utilization methods, the process of separating acetophenone in the present invention is simple and has low energy consumption. After further resource utilization, there is basically no solid waste emission, and the final product has high added value. It is a green, safe, and economically effective phenol-ketone tar resource utilization method.

[0045] (3) The present invention uses industrial waste such as phenol ketone tar as the raw material for preparing petroleum fracturing proppants, which greatly reduces the use cost of petroleum fracturing proppants and achieves a significant reduction or zero emission of phenol ketone tar during the comprehensive utilization process. In addition, cumylphenol is further prepared into phenolic epoxy resin after condensation of phenolic aldehyde. Due to the presence of branched groups, the comprehensive performance of the obtained petroleum fracturing proppants is effectively improved. DETAILED DESCRIPTION

[0046] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0047] A certain embodiment of the present invention provides a method for comprehensive utilization of phenol-ketone tar, the method comprising at least the following steps:

[0048] (1) mixing phenol-ketone tar and an acidic catalyst to carry out a first temperature-raising reaction, and then adding an aldehyde compound to carry out a second temperature-raising reaction to obtain a phenolic resin mixture;

[0049] (2) subjecting the phenolic resin mixture obtained in step (1) to negative pressure distillation to obtain a tower top material and a tower bottom material; wherein the tower top material is separated into layers to obtain acetophenone, and the tower bottom material comprises a phenolic resin;

[0050] (3) mixing a phase transfer catalyst, epichlorohydrin and the phenolic resin obtained in step (2) to carry out a ring-opening reaction, then adding a base to carry out a ring-closing reaction, and separating to obtain a phenolic epoxy resin;

[0051] (4) mixing the curing agent, the accelerator and the phenolic epoxy resin obtained in step (3) and stirring the mixture to obtain an oil fracturing proppant.

[0052] The phenol-ketone tar contains at least phenol, acetophenone, α-methylstyrene dimer and cumylphenol.

[0053] The present invention first uses an acidic catalyst to decompose α-methylstyrene dimer in phenol-ketone tar into monomers, which are then condensed with phenol to generate cumylphenol. Then, an aldehyde compound is added to react with phenol and cumylphenol to generate phenolic resin. After the phenol is consumed, the azeotropic composition of phenol and acetophenone is broken, thereby significantly reducing the difficulty of purifying acetophenone. After the acetophenone is extracted, the remaining tar is synthesized into phenolic epoxy resin, and then into a petroleum fracturing proppant.

[0054] Compared with conventional phenol-ketone tar resource utilization methods, the acetophenone separation process of the present invention is simple and has low energy consumption. After further resource utilization, there is basically no solid waste emission, and the final product has high added value. It is a green, safe and economically beneficial phenol-ketone tar resource utilization method.

[0055] In addition, the present invention uses industrial waste such as phenol-ketone tar as a raw material for preparing petroleum fracturing proppants, which greatly reduces the use cost of petroleum fracturing proppants and achieves a significant reduction or zero emission of phenol-ketone tar during the comprehensive utilization process. Cumylphenol is further condensed with phenolic aldehyde to produce phenolic epoxy resin. Due to the presence of branched groups, the comprehensive performance of the obtained petroleum fracturing proppant is effectively improved.

[0056] In certain embodiments, the phenol-ketone tar is a heavy component tar produced by the cumene process to produce phenol and acetone.

[0057] In certain embodiments, the acidic catalyst in step (1) comprises any one of sulfuric acid, hydrochloric acid, benzenesulfonic acid or methylbenzenesulfonic acid, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of sulfuric acid and hydrochloric acid, a combination of hydrochloric acid and benzenesulfonic acid, a combination of benzenesulfonic acid and methylbenzenesulfonic acid, a combination of sulfuric acid, hydrochloric acid and benzenesulfonic acid, a combination of hydrochloric acid, benzenesulfonic acid and methylbenzenesulfonic acid, or a combination of sulfuric acid, hydrochloric acid, benzenesulfonic acid and methylbenzenesulfonic acid.

[0058] In certain embodiments, the amount of the acidic catalyst added in step (1) is 0.5%-10% of the mass of the phenol-ketone tar, for example, it can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0059] In certain embodiments, the target temperature of the first temperature-raising reaction in step (1) is 60°C-120°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C, and the reaction time is 1h-6h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0060] In certain embodiments, the aldehyde compound in step (1) includes aqueous formaldehyde solution and / or paraformaldehyde.

[0061] In some embodiments, the concentration of the formaldehyde aqueous solution is 30%-40%, for example, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0062] In some embodiments, the amount of the aldehyde compound added in step (1) is 1%-100% of the mass of the phenol-ketone tar, for example, it can be 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0063] In certain embodiments, the target temperature of the second temperature-raising reaction in step (1) is 80°C-130°C, for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C or 130°C, and the reaction time is 2h-8h, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0064] In certain embodiments, the number of theoretical plates of the negative pressure distillation in step (2) is 5-50, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0065] In certain embodiments, the operating pressure of the negative pressure distillation in step (2) is 1 kPa-60 kPa, for example, it can be 1 kPa, 5 kPa, 10 kPa, 15 kPa, 20 kPa, 25 kPa, 30 kPa, 35 kPa, 40 kPa, 45 kPa, 50 kPa, 55 kPa or 60 kPa, but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0066] In certain embodiments, the reflux ratio of the negative pressure distillation in step (2) is 0.1-5, for example, it can be 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0067] In certain embodiments, the phase transfer catalyst in step (3) comprises benzyltriethylammonium chloride.

[0068] In certain embodiments, the mixing mass ratio of the phase transfer catalyst, epichlorohydrin and phenolic resin in step (3) is (0.01-0.02):(5-6):1, for example, it can be 0.01:5:1, 0.01:5.2:1, 0.01:5.4:1, 0.02:5.6:1, 0.02:5.8:1 or 0.02:6:1, but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0069] In certain embodiments, the base in step (3) comprises a sodium hydroxide solution having a concentration of 45%-50%, for example, the concentration may be 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5% or 50%, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0070] In certain embodiments, the amount of base added in step (3) is 40%-50% of the mass of the phenolic resin, for example, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50%, but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0071] In certain embodiments, the curing agent in step (4) includes any one or a combination of at least two of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 4,4'-diaminodiphenylmethane, m-phenylenediamine, m-phenylenediamine or 4,4'-diaminodiphenyl sulfone. Typical but non-limiting combinations include a combination of methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, a combination of methyltetrahydrophthalic anhydride and tetrahydrophthalic anhydride. a combination of tetrahydrophthalic anhydride and maleic anhydride, a combination of maleic anhydride and succinic anhydride, a combination of succinic anhydride and phthalic anhydride, a combination of phthalic anhydride and trimellitic anhydride, a combination of trimellitic anhydride and pyromellitic dianhydride, a combination of pyromellitic dianhydride and 4,4'-diaminodiphenylmethane, a combination of 4,4'-diaminodiphenylmethane and meta-phenylenediamine, a combination of meta-phenylenediamine and meta-phenylenediamine, or a combination of meta-phenylenediamine and 4,4'-diaminodiphenyl sulfone.

[0072] In certain embodiments, the accelerator in step (4) includes any one or a combination of at least two of 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, phenol, o-cresol, or resorcinol. Typical but non-limiting combinations include a combination of 2,4,6-tris(dimethylaminomethyl)phenol and N,N-dimethylbenzylamine, a combination of N,N-dimethylbenzylamine and 2-ethyl-4-methylimidazole, a combination of 2-ethyl-4-methylimidazole and phenol, a combination of phenol and o-cresol, or a combination of o-cresol and resorcinol.

[0073] In certain embodiments, the mixing mass ratio of the curing agent, accelerator and phenolic epoxy resin in step (4) is (0.1-1):(0.01-0.1):1, for example, it can be 0.1:0.1:1, 0.2:0.09:1, 0.3:0.08:1, 0.4:0.07:1, 0.5:0.06:1, 0.6:0.05:1, 0.7:0.04:1, 0.8:0.03:1, 0.9:0.02:1 or 1:0.01:1, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0074] In certain embodiments, the stirring reaction in step (4) is carried out in a dispersant.

[0075] In certain embodiments, the dispersant includes silicone oil and / or dimethicone.

[0076] In certain embodiments, the mixing mass ratio of the dispersant and the phenolic epoxy resin is (30-60):1, for example, it can be 30:1, 35:1, 40:1, 45:1, 50:1, 55:1 or 60:1, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0077] In certain embodiments, the stirring reaction temperature in step (4) is 120°C-180°C, for example, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C or 180°C, and the time is 10 min-300 min, for example, 10 min, 50 min, 100 min, 150 min, 200 min, 250 min or 300 min, but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0078] In certain embodiments, the phenol-ketone tar is subjected to a deweighting treatment and / or phenol is added before comprehensive utilization.

[0079] An embodiment of the present invention also provides a petroleum fracturing proppant prepared by the method for comprehensive utilization of phenol-ketone tar described in any of the above embodiments, wherein the glass transition temperature of the petroleum fracturing proppant is 155°C-190°C, for example, it can be 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C or 190°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0080] In the present invention, the phenol-ketone tar used in each embodiment and comparative example is all from the phenol-ketone device of Jiangsu Ruiheng New Materials Co., Ltd., and the specific composition of the phenol-ketone tar is as follows: phenol content 7.1%, acetophenone content 20.9%, α-methylstyrene dimer content 8.5%, 2-cumylphenol content 4.0%, 4-cumylphenol content 21.1%, and the rest are unavoidable impurities.

[0081] Unless otherwise specified, the concentration or content of various materials in the present invention refers to mass concentration or mass percentage.

[0082] Example 1

[0083] This embodiment provides a method for comprehensive utilization of phenol-ketone tar, which specifically comprises the following steps:

[0084] (1) Weighing 150 g of phenol-ketone tar and 4.5 g of sulfuric acid, respectively, mixed them and heated to 85° C., kept warm for 3 h, then added 20 g of a 37% formaldehyde aqueous solution, and continued heating to 100° C. for 3 h to obtain a phenolic resin mixture;

[0085] (2) transferring the phenolic resin mixture obtained in step (1) into a distillation column for negative pressure distillation at an operating pressure of 10 kPa, a theoretical plate number of 20, and a reflux ratio of 2 to obtain a top material and a bottom material; wherein the top material is a mixture of acetophenone and water, and after standing and stratification, 26.3 g of acetophenone is extracted; and the bottom material is a phenolic resin totaling 128 g;

[0086] (3) 1.7 g of benzyltriethylammonium chloride and 733 g of epichlorohydrin were sequentially added to the phenolic resin to carry out a ring-opening etherification reaction for 3 h, followed by the addition of 55 g of a 48% sodium hydroxide solution, and a water-containing ring-closing reaction under negative pressure. The epichlorohydrin was then removed, and toluene was added to wash the mixture, and the mixture was separated. After toluene was recovered from the oil layer, a phenolic epoxy resin having an epoxy equivalent of 345 g / mol was obtained.

[0087] (4) 100 g of phenolic epoxy resin, 85 g of methyltetrahydrophthalic anhydride, and 3 g of 2,4,6-tris(dimethylaminomethyl)phenol were weighed separately, added to 4 kg of silicone oil, and stirred at 160 °C for 60 min. After filtering, washing, and drying, an oil fracturing proppant was obtained.

[0088] Example 2

[0089] This embodiment provides a method for comprehensive utilization of phenol-ketone tar, which specifically comprises the following steps:

[0090] (1) Weigh 150 g of phenol-ketone tar, 2.5 g of sulfuric acid, and 2.5 g of p-toluenesulfonic acid, respectively, mix them, heat them to 90°C, and keep them warm for 4 h. Then, add 5 g of paraformaldehyde, and continue heating to 110°C for 2 h to obtain a phenolic resin mixture;

[0091] (2) transferring the phenolic resin mixture obtained in step (1) into a distillation column for negative pressure distillation at an operating pressure of 5 kPa, a theoretical plate number of 10, and a reflux ratio of 3 to obtain a top material and a bottom material; wherein the top material is a mixture of acetophenone and water, and after standing and stratification, 28.8 g of acetophenone is extracted; and the bottom material is a phenolic resin totaling 125 g;

[0092] (3) 1.7 g of benzyltriethylammonium chloride and 716 g of epichlorohydrin were sequentially added to the phenolic resin to carry out a ring-opening etherification reaction for 3 h, followed by the addition of 55 g of a 48% sodium hydroxide solution, and a water-containing ring-closing reaction under negative pressure. The epichlorohydrin was then removed, and toluene was added to wash the mixture, and the mixture was separated. After toluene was recovered from the oil layer, a phenolic epoxy resin having an epoxy equivalent of 317 g / mol was obtained.

[0093] (4) 100 g of phenolic epoxy resin, 15 g of m-phenylenediamine, and 3 g of o-cresol were weighed separately, added to 4 kg of dimethyl silicone oil, and stirred at 150 °C for 240 min. After filtering, washing, and drying, an oil fracturing proppant was obtained.

[0094] Example 3

[0095] This embodiment provides a method for comprehensive utilization of phenol-ketone tar, which specifically comprises the following steps:

[0096] (1) Weighing 150 g of phenol-ketone tar, 2 g of hydrochloric acid, and 6 g of benzenesulfonic acid, respectively, mixed them, heated to 120° C., and kept warm for 5 h. Then, 9 g of paraformaldehyde was added, and the temperature was raised to 105° C. and reacted for 3 h to obtain a phenolic resin mixture;

[0097] (2) transferring the phenolic resin mixture obtained in step (1) into a distillation column for negative pressure distillation at an operating pressure of 25 kPa, a theoretical plate number of 20, and a reflux ratio of 3 to obtain a top material and a bottom material; wherein the top material is a mixture of acetophenone and water, and after standing and stratification, 28.9 g of acetophenone is extracted; and the bottom material is a phenolic resin totaling 127 g;

[0098] (3) 1.7 g of benzyltriethylammonium chloride and 715 g of epichlorohydrin were sequentially added to the phenolic resin to carry out a ring-opening etherification reaction for 3 h, followed by the addition of 55 g of a 48% sodium hydroxide solution, and a water-containing ring-closing reaction under negative pressure. The epichlorohydrin was then removed, and toluene was added to wash the mixture, and the mixture was separated. After toluene was recovered from the oil layer, a phenolic epoxy resin having an epoxy equivalent of 290 g / mol was obtained.

[0099] (4) 100 g of phenolic epoxy resin, 28 g of 4,4'-diaminodiphenylmethane, and 2.5 g of phenol were weighed separately, added to 3 kg of silicone oil, and stirred at 160°C for 120 min. After filtering, washing, and drying, a petroleum fracturing proppant was obtained.

[0100] Example 4

[0101] This embodiment provides a method for comprehensive utilization of phenol-ketone tar, which specifically comprises the following steps:

[0102] (1) 80 g of phenol-ketone tar, 20 g of phenol, and 4 g of sulfuric acid were weighed separately, mixed, and heated to 105° C. for 2.5 h. Then, 6 g of paraformaldehyde was added, and the temperature was raised to 95° C. for 5 h to obtain a phenolic resin mixture;

[0103] (2) transferring the phenolic resin mixture obtained in step (1) into a distillation column for negative pressure distillation at an operating pressure of 30 kPa, a theoretical plate number of 30, and a reflux ratio of 1 to obtain a top material and a bottom material; wherein the top material is a mixture of acetophenone and water, and after standing and stratification, 15.5 g of acetophenone is extracted; and the bottom material is a phenolic resin totaling 90.5 g;

[0104] (3) 1.3 g of benzyltriethylammonium chloride and 540 g of epichlorohydrin were sequentially added to the phenolic resin to carry out a ring-opening etherification reaction for 3 h, followed by the addition of 40 g of a 48% sodium hydroxide solution, and a water-containing ring-closing reaction under negative pressure. The epichlorohydrin was then removed, and toluene was added to wash the mixture, and the mixture was separated. After toluene was recovered from the oil layer, a phenolic epoxy resin having an epoxy equivalent of 283 g / mol was obtained.

[0105] (4) 100 g of phenolic epoxy resin, 55 g of succinic anhydride, and 3.5 g of 2,4,6-tris(dimethylaminomethyl)phenol were weighed separately, added to 6 kg of dimethyl silicone oil, and stirred at 150 °C for 90 min. After filtering, washing, and drying, an oil fracturing proppant was obtained.

[0106] Example 5

[0107] This embodiment provides a method for comprehensive utilization of phenol-ketone tar, which specifically comprises the following steps:

[0108] (1) Weighing 776 g of phenol-ketone tar, performing a de-weighting treatment at a pressure of 0.5 kPa, and collecting a de-weighting fraction totaling 623 g, wherein: phenol content is 8.7%, acetophenone content is 25.5%, α-methylstyrene dimer content is 10.4%, 2-cumylphenol content is 4.9%, and 4-cumylphenol content is 25.8%;

[0109] (2) Weighing 115 g of the de-heavy fraction, 1 g of sulfuric acid, and 3.5 g of benzenesulfonic acid, respectively, mixed them, heated to 110°C, and kept warm for 1.5 h. Then, 5 g of paraformaldehyde was added, and the temperature was raised to 85°C for reaction for 2 h to obtain a phenolic resin mixture;

[0110] (3) transferring the phenolic resin mixture obtained in step (2) into a distillation column for negative pressure distillation at an operating pressure of 40 kPa, a theoretical plate number of 50, and a reflux ratio of 0.5 to obtain a top material and a bottom material; wherein the top material is a mixture of acetophenone and water, and after standing and stratification, 27.4 g of acetophenone is extracted; and the bottom material is a phenolic resin totaling 95 g;

[0111] (4) 1.4 g of benzyltriethylammonium chloride and 550 g of epichlorohydrin were sequentially added to the phenolic resin to carry out a ring-opening etherification reaction for 3 h, followed by the addition of 42 g of a 48% sodium hydroxide solution, and a water-containing ring-closing reaction under negative pressure. The epichlorohydrin was then removed, and the mixture was washed with water after adding toluene to separate the layers. The toluene was recovered from the oil layer to obtain a phenolic epoxy resin with an epoxy equivalent of 282 g / mol.

[0112] (5) 100 g of phenolic epoxy resin, 72 g of phthalic anhydride, and 1.5 g of N,N-dimethylbenzylamine were weighed separately, added to 4 kg of silicone oil, and stirred at 180 °C for 180 min. After filtering, washing, and drying, an oil fracturing proppant was obtained.

[0113] Example 6

[0114] This embodiment provides a method for comprehensive utilization of phenol-ketone tar, which specifically comprises the following steps:

[0115] (1) 90 g of the de-heavy fraction (the content of the components is the same as in Example 5), 60 g of phenol, and 6 g of sulfuric acid were weighed, mixed, and heated to 85° C. for 3 h. 10 g of paraformaldehyde was then added, and the temperature was further raised to 105° C. for reaction for 2 h to obtain a phenolic resin mixture;

[0116] (2) transferring the phenolic resin mixture obtained in step (1) into a distillation column for negative pressure distillation at an operating pressure of 50 kPa, a theoretical plate number of 20, and a reflux ratio of 1 to obtain a top material and a bottom material; wherein the top material is a mixture of acetophenone and water, and after standing and stratification, 18.2 g of acetophenone is extracted; and the bottom material is a phenolic resin totaling 127 g;

[0117] (3) 1.7 g of benzyltriethylammonium chloride and 730 g of epichlorohydrin were sequentially added to the phenolic resin to carry out a ring-opening etherification reaction for 3 h, followed by the addition of 60 g of a 48% sodium hydroxide solution, and a water-containing ring-closing reaction under negative pressure. The epichlorohydrin was then removed, and toluene was added to wash the mixture, and the mixture was separated. After toluene was recovered from the oil layer, a phenolic epoxy resin having an epoxy equivalent of 250 g / mol was obtained.

[0118] (4) 100 g of phenolic epoxy resin, 75 g of tetrahydrophthalic anhydride, and 5 g of 2-ethyl-4-methylimidazole were weighed separately, added to 4 kg of silicone oil, and stirred at 150° C. for 60 min. After filtering, washing, and drying, an oil fracturing proppant was obtained.

[0119] Example 7

[0120] This embodiment provides a method for comprehensive utilization of phenol-ketone tar, which specifically comprises the following steps:

[0121] (1) 75 g of the de-heavy fraction (the same component content as in Example 5), 75 g of phenol, 2.5 g of sulfuric acid, and 3 g of benzenesulfonic acid were weighed, mixed, and heated to 100° C. for 2 h. 63 g of a 37% formaldehyde aqueous solution was then added, and the temperature was further raised to 105° C. for reaction for 2 h to obtain a phenolic resin mixture;

[0122] (2) transferring the phenolic resin mixture obtained in step (1) into a distillation column for negative pressure distillation at an operating pressure of 15 kPa, a theoretical plate number of 15, and a reflux ratio of 1 to obtain a top material and a bottom material; wherein the top material is a mixture of acetophenone and water, and after standing and stratification, 17.6 g of acetophenone is extracted; and the bottom material is a phenolic resin totaling 136 g;

[0123] (3) 1.8 g of benzyltriethylammonium chloride and 790 g of epichlorohydrin were sequentially added to the phenolic resin to carry out a ring-opening etherification reaction for 3 h, followed by the addition of 82 g of a 48% sodium hydroxide solution, and a water-containing ring-closing reaction under negative pressure. The epichlorohydrin was then removed, and toluene was added to wash the mixture, and the mixture was separated. After toluene was recovered from the oil layer, a phenolic epoxy resin having an epoxy equivalent of 248 g / mol was obtained.

[0124] (4) 100 g of phenolic epoxy resin, 60 g of maleic anhydride, and 6 g of 2,4,6-tris(dimethylaminomethyl)phenol were weighed separately, added to 4 kg of dimethyl silicone oil, and stirred at 155 °C for 75 min. After filtering, washing, and drying, an oil fracturing proppant was obtained.

[0125] Comparative Example 1

[0126] This comparative example provides a method for preparing a petroleum fracturing proppant, specifically comprising: weighing 100 g of E51 epoxy resin, 85 g of methyltetrahydrophthalic anhydride, and 3 g of 2,4,6-tris(dimethylaminomethyl)phenol, respectively, adding the mixture to 4 kg of silicone oil, stirring and reacting the mixture at 160° C. for 60 min, and filtering, washing, and drying the mixture to obtain a petroleum fracturing proppant.

[0127] After testing, the purity and yield of the acetophenone obtained in Examples 1-7 and the physical properties of the petroleum fracturing proppants obtained in Examples 1-7 and Comparative Example 1 are shown in Table 1 below.

[0128] Table 1

[0129]

[0130] Thus, the present invention first uses an acidic catalyst to decompose α-methylstyrene dimer in phenol-ketone tar into monomers, which are then condensed with phenol to form cumylphenol. Then, an aldehyde compound is added to react with phenol and cumylphenol to form a phenolic resin. After the phenol is consumed, the azeotropic composition of phenol and acetophenone is broken, thereby significantly reducing the difficulty of purifying acetophenone. After the acetophenone is extracted, the remaining tar is synthesized into a phenolic epoxy resin, and then into a petroleum fracturing proppant.

[0131] Compared with conventional phenol-ketone tar resource utilization methods, the acetophenone separation process of the present invention is simple and has low energy consumption. After further resource utilization, there is basically no solid waste emission, and the final product has high added value. It is a green, safe and economically beneficial phenol-ketone tar resource utilization method.

[0132] In addition, the present invention uses industrial waste such as phenol-ketone tar as a raw material for preparing petroleum fracturing proppants, which greatly reduces the use cost of petroleum fracturing proppants and achieves a significant reduction or zero emission of phenol-ketone tar during the comprehensive utilization process. Cumylphenol is further condensed with phenolic aldehyde to produce phenolic epoxy resin. Due to the presence of branched groups, the comprehensive performance of the obtained petroleum fracturing proppant is effectively improved.

[0133] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for comprehensive utilization of phenol-ketone tar, characterized in that: The method comprises at least the following steps: (1) mixing phenol-ketone tar and an acidic catalyst to carry out a first temperature-raising reaction, and then adding an aldehyde compound to carry out a second temperature-raising reaction to obtain a phenolic resin mixture; (2) subjecting the phenolic resin mixture obtained in step (1) to negative pressure distillation to obtain a tower top material and a tower bottom material; wherein the tower top material is separated into layers to obtain acetophenone, and the tower bottom material comprises a phenolic resin; (3) mixing a phase transfer catalyst, epichlorohydrin and the phenolic resin obtained in step (2) to carry out a ring-opening reaction, then adding a base to carry out a ring-closing reaction, and separating to obtain a phenolic epoxy resin; (4) mixing a curing agent, an accelerator, and the phenolic epoxy resin obtained in step (3) and stirring the mixture to obtain an oil fracturing proppant; The phenol-ketone tar contains at least phenol, acetophenone, α-methylstyrene dimer and cumylphenol.

2. The method for comprehensive utilization of phenol-ketone tar according to claim 1, wherein The phenol-ketone tar is a heavy component tar produced by the cumene process to produce phenol and acetone.

3. The method for comprehensive utilization of phenol-ketone tar according to claim 1 or 2, characterized in that, The acidic catalyst in step (1) comprises any one of sulfuric acid, hydrochloric acid, benzenesulfonic acid or dimethylbenzenesulfonic acid, or a combination of at least two thereof; And / or, the amount of the acidic catalyst added in step (1) is 0.5%-10% of the mass of the phenol-ketone tar; And / or, the target temperature of the first temperature-raising reaction in step (1) is 60° C.-120° C., and the reaction time is 1 h-6 h.

4. The method for comprehensive utilization of phenol-ketone tar according to claim 3, wherein: The aldehyde compound in step (1) includes formaldehyde solution and / or paraformaldehyde; Wherein, the concentration of the formaldehyde aqueous solution is 30%-40%; And / or, the amount of the aldehyde compound added in step (1) is 1%-100% of the mass of the phenol-ketone tar; And / or, the target temperature of the second temperature-raising reaction in step (1) is 80° C.-130° C., and the reaction time is 2 h-8 h.

5. The method for comprehensive utilization of phenol-ketone tar according to claim 1 or 2, characterized in that: The number of theoretical plates of the negative pressure distillation in step (2) is 5-50; And / or, the operating pressure of the negative pressure distillation in step (2) is 1 kPa-60 kPa; And / or, the reflux ratio of the negative pressure distillation in step (2) is 0.1-5.

6. The method for comprehensive utilization of phenol-ketone tar according to claim 1 or 2, characterized in that: The phase transfer catalyst in step (3) comprises benzyltriethylammonium chloride; And / or, the mixing mass ratio of the phase transfer catalyst, epichlorohydrin and phenolic resin in step (3) is (0.01-0.02):(5-6):1; And / or, the base in step (3) comprises a sodium hydroxide solution with a concentration of 45%-50%; And / or, the amount of the base added in step (3) is 40%-50% of the mass of the phenolic resin.

7. The method for comprehensive utilization of phenol-ketone tar according to claim 1 or 2, characterized in that: The curing agent in step (4) comprises any one or a combination of at least two of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 4,4'-diaminodiphenylmethane, m-phenylenediamine, m-phenylenediamine or 4,4'-diaminodiphenyl sulfone; And / or, the accelerator in step (4) comprises any one or a combination of at least two of 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, phenol, o-cresol or resorcinol; And / or, the mixing mass ratio of the curing agent, accelerator and phenolic epoxy resin in step (4) is (0.1-1):(0.01-0.1):

1.

8. The method for comprehensive utilization of phenol-ketone tar according to claim 1 or 2, characterized in that: The stirring reaction in step (4) is carried out in a dispersant; Wherein, the dispersant includes silicone oil and / or dimethyl silicone oil; And / or, the mixing mass ratio of the dispersant and the phenolic epoxy resin is (30-60):1; And / or, the stirring reaction in step (4) is carried out at a temperature of 120° C. to 180° C. and for a time of 10 min to 300 min.

9. The method for comprehensive utilization of phenol-ketone tar according to claim 1 or 2, characterized in that: The phenol-ketone tar is subjected to a weight removal treatment and / or phenol is added before comprehensive utilization.

10. A petroleum fracturing proppant prepared by the method for comprehensive utilization of phenol-ketone tar according to any one of claims 1 to 9, characterized in that: The glass transition temperature of the petroleum fracturing proppant is 155°C-190°C.

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