A method for preparing coal water slurry additive by using styrene tar

Abstract

The application discloses a method for preparing a water coal slurry additive by using styrene tar, and the styrene tar generated by a PO / SM device in a park is subjected to a sulfonation reaction with waste sulfuric acid generated by a hydrogen chloride oxidation device, and then is subjected to a hydrolysis reaction, a condensation reaction and a neutralization reaction, so that a high-efficiency water coal slurry additive is obtained. Compared with traditional additives such as lignin sulfonic acid and naphthalene, the water coal slurry additive has the advantages of better viscosity reduction effect and better fluidity, can be used for preparing high-concentration water coal slurry, realizes resource recycling of waste, reduces carbon emission and reduces environmental pollution.

Description

Technical Field

[0001] This invention belongs to the field of coal-water slurry gasification, and specifically relates to a method for preparing coal-water slurry additives using styrene tar. Background Technology

[0002] Coal-water slurry gasification is a clean coal technology that emerged in the 1980s. It involves preparing a coal-water slurry with coal, water, and a small amount of chemical additives, which is then reacted with oxygen in a gasifier. The resulting CO and H2 are used industrially. A high-performance coal-water slurry should have high concentration, low viscosity, good fluidity, and long stability time. Under the same conditions, the lower the viscosity and the better the fluidity of the coal-water slurry, the higher its slurry concentration, thereby reducing the gasification unit consumption.

[0003] The PO / SM unit uses ethylbenzene as raw material to produce propylene oxide and styrene. During the styrene production process, a large amount of tar accumulates, with a mass composition of approximately 1-3% styrene, 10-20% diphenylbutene, 1-10% diethylpropylphenol, and 60-80% styrene tricyclic and higher polymers. Currently, this tar is mainly sent for incineration. Simultaneously, the chlorination-hydrogenation unit produces approximately 75% waste sulfuric acid, which requires waste liquid treatment, resulting in high costs. Research on the resource recovery and utilization of these waste liquids is limited in the industry, failing to effectively integrate resources to form high-value-added chemical products, thereby reducing environmental pollution and lowering production costs.

[0004] CN106905195 discloses a method for preparing sulfonates from styrene tar through recycling. The method involves using concentrated sulfuric acid / fuming sulfuric acid, chlorosulfonic acid, or sulfur trioxide as sulfonating agents to sulfonate styrene tar. After purification, the sulfonate product is obtained, primarily used as a water-reducing agent for silicate inorganic materials like cement. However, its effectiveness as an additive in coal-water slurry is poor. This is because high-efficiency coal-water slurry additives require a certain degree of polymerization of the sulfonates, while the polymer component in this patented sulfonate comes only from the heavy components of the raw material styrene tar, accounting for less than 50%, resulting in a low degree of polymerization. Furthermore, the sulfonating agent used in this patent needs to be purchased, increasing production costs. Summary of the Invention

[0005] The main objective of this invention is to provide a method for preparing coal-water slurry additives using PO / SM tar, which can effectively integrate waste liquid and produce high-value-added, high-efficiency coal-water slurry additives. The coal-water slurry additives prepared by this method can effectively improve the performance of coal-water slurry, increase its concentration, reduce gasifier operating costs, decrease environmental pollution, and lower production costs.

[0006] Therefore, the solution adopted in this invention is as follows:

[0007] On one hand, the present invention provides a method for preparing coal-water slurry additives using PO / SM tar, the method comprising: using styrene tar as raw material, sequentially undergoing sulfonation reaction, hydrolysis reaction, condensation reaction and neutralization reaction, and finally obtaining a high-efficiency coal-water slurry additive.

[0008] In this invention, the styrene tar comes from a PO / SM unit, and its raw material composition is styrene tricyclic and above polymer: 60-80%, diphenyl-butene: 10-20%, 2,4-diethylphenyl-phenol: 1-10%, and styrene: 1-3%.

[0009] The sulfonating agent used in the sulfonation reaction is waste sulfuric acid produced by the chlorination and hydrogenation unit. Preferably, the waste sulfuric acid produced by the chlorination and hydrogenation unit contains 70wt% to 90wt% sulfuric acid.

[0010] The hydrolysis agent used in the hydrolysis reaction process is all the distilled acid solution produced during the sulfonation process and the industrial water in the park.

[0011] The condensing agent used in the condensation reaction is a formaldehyde solution;

[0012] The neutralizing agent used in the neutralization reaction is an alkaline liquid such as industrial sodium hydroxide or potassium hydroxide.

[0013] Preferably, the sulfonation reaction is carried out in a reaction vessel equipped with a distillation apparatus;

[0014] Preferably, the mass ratio of the styrene tar to the waste sulfuric acid produced by the chlorination and hydrogenation unit is 1:1.4 to 1.6;

[0015] Preferably, the sulfonation reaction temperature is 120℃~180℃; the sulfonation reaction time is 2h~6h.

[0016] In this invention, the sulfonation reaction process produces a distilled acid solution due to the presence of an azeotrope with water in the tar. The mass ratio of this acid solution to the raw material styrene tar is 0.2 to 0.25:1.

[0017] Preferably, the mass ratio of water to styrene tar in the hydrolysis reaction is 0.25–0.35:1.

[0018] Preferably, the hydrolysis reaction temperature is 100℃~150℃; the hydrolysis reaction time is 0.5h~1.5h.

[0019] Preferably, the formaldehyde solution has a mass concentration of 32% to 37%;

[0020] Preferably, the mass ratio of formaldehyde solution to styrene in the condensation reaction is 0.2–0.3:1.

[0021] Preferably, the temperature of the condensation reaction is 105℃~115℃; the time of the condensation reaction is 1h~2h.

[0022] Preferably, the mass concentration of the industrial sodium hydroxide alkaline solution is 30% to 35%;

[0023] Preferably, by controlling the amount of industrial sodium hydroxide alkaline solution added, the pH of the neutralization product is between 7.0 and 9.0;

[0024] Preferably, the initial temperature of the neutralization reaction is 40℃~50℃; the neutralization reaction time is 1h~2h.

[0025] On the other hand, the present invention also provides a coal-water slurry additive prepared by the above method.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] (1) This invention develops a high-efficiency coal-water slurry additive by recycling styrene tar from PO / SM plants, which improves the added value of PO / SM tar. Compared with traditional additives such as lignin sulfonic acid and naphthalene, it has the advantages of better viscosity reduction and better fluidity. It can be used to prepare high-concentration coal-water slurry, realize the resource recycling of waste, reduce carbon emissions, and reduce environmental pollution.

[0028] (2) Through distillation and sulfonation, 70-90% of the waste sulfuric acid in the chlorination-hydrogenation unit is given a highly efficient sulfonation effect, replacing industrial 98% concentrated sulfuric acid / fuming sulfuric acid, etc., effectively reducing the production cost of this coal-water slurry additive. Simultaneously, the distilled acid produced during the distillation process can be directly used for the hydrolysis reaction, generating no waste. The sulfonation reaction is accompanied by the distillation process, allowing 70%-90% of the waste sulfuric acid to be used as the sulfonating agent, eliminating the need to purchase 98% concentrated sulfuric acid / fuming sulfuric acid, etc., effectively reducing the production cost of the coal-water slurry additive. Furthermore, the distilled acid produced during the distillation process can be directly used for the hydrolysis reaction, thus preventing waste liquid generation. The condensation process uses industrial formaldehyde to polymerize the sulfonated product, effectively increasing the chain length and degree of polymerization, thereby greatly improving the dispersibility of the coal-water slurry additive. Detailed Implementation

[0029] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. Raw materials and sources:

[0030] Styrene tar: Styrene tar from Wanhua PO / SM unit

[0031] 70-90% sulfuric acid: Sulfuric acid from Wanhua HCl oxidation unit

[0032] Industrial naphthalene: Sinopharm Chemical Reagents;

[0033] 30-35% Sodium Hydroxide: By-product alkali solution from Wanhua Chlor-Alkali

[0034] 32-37% formaldehyde: Wanhua formaldehyde removal equipment products

[0035] Pulverized coal, Shenhua Group Shenyou No. 2 coal sample

[0036] Test method:

[0037] The following test methods are used in the various embodiments and comparative examples of this invention:

[0038] The concentration, viscosity, and flowability of the coal-water slurry, as well as the testing methods, were all conducted in accordance with GB / T 18855-2008. Viscometer: Model NXS-4C (National Coal-Water Slurry Engineering Technology Development Center).

[0039] Rapid Moisture Analyzer: Model M35M (Sartorius Scientific Instruments (Beijing) Co., Ltd.)

[0040] Detection of sulfonic acid group content: Wantong potentiometric titration 905, Wantong ion chromatography 930

[0041] Example 1

[0042] 100g of styrene tar from a PO / SM unit was placed in a round-bottom flask equipped with a stirrer and distillation apparatus. The temperature was raised to 80°C, and 140g of 90% sulfuric acid from a hydrogen peroxide chlorination unit was added dropwise to the flask. The temperature was then raised to 120°C for a sulfonation reaction for 2 hours, producing 20g of distilled acid solution. After sulfonation, the temperature was lowered to 140°C, and the distillation apparatus was shut off. 20g of distilled acid solution and 5g of water were added dropwise to initiate a hydrolysis reaction for 0.5 hours. After hydrolysis, the temperature was lowered to 110°C, and 25g of 32% formaldehyde aqueous solution was added dropwise to initiate a condensation reaction for 2 hours. After condensation, the temperature was lowered to 40°C, and 32% industrial sodium hydroxide alkali solution was added dropwise, ultimately yielding a coal-water slurry additive with a pH of 7 and a sulfonic acid group content of 12.5%.

[0043] Preparation of coal-water slurry: Take 79.6g of coal powder and 0.2g (dry basis) of the coal-water slurry additive prepared above, dilute with water to 100g, and stir evenly to obtain a flowable coal-water slurry. The flowability was tested according to the standard method and was B+. The apparent viscosity of the coal-water slurry at 25℃ was measured to be 867mPa·s using a viscometer, and the concentration of the coal-water slurry was measured to be 67.7wt% using a rapid moisture analyzer.

[0044] Example 2

[0045] 100g of styrene tar from a PO / SM unit was placed in a round-bottom flask equipped with a stirrer and distillation apparatus. The temperature was raised to 80°C, and 150g of 70% sulfuric acid from a hydrogen peroxide chlorination unit was added dropwise to the flask. The temperature was then raised to 130°C for a sulfonation reaction for 3 hours, producing 22g of distilled acid. After sulfonation, the temperature was lowered to 110°C, and the distillation apparatus was shut off. 22g of distilled acid and 13g of water were added dropwise to initiate a hydrolysis reaction for 1 hour. After hydrolysis, the temperature was maintained at 110°C, and 30g of a 37% formaldehyde aqueous solution was added dropwise to initiate a condensation reaction for 1.5 hours. After condensation, the temperature was lowered to 45°C, and 35% industrial sodium hydroxide alkali solution was added dropwise, ultimately yielding a coal-water slurry additive with a pH of 8 and a sulfonic acid group content of 12.9%.

[0046] Preparation of coal-water slurry: Take 80.1g of coal powder and 0.2g (dry basis) of the coal-water slurry additive prepared above, dilute with water to 100g, and stir evenly to obtain a flowable coal-water slurry. The flowability was tested according to the standard method and was rated as B. The apparent viscosity of the coal-water slurry at 25℃ was measured to be 872mPa·s using a viscometer, and the concentration of the coal-water slurry was measured to be 68.1wt% using a rapid moisture analyzer.

[0047] Example 3

[0048] 100g of styrene tar from a PO / SM unit was placed in a round-bottom flask equipped with a stirrer and distillation apparatus. The temperature was raised to 80°C, and 160g of 80% sulfuric acid from a hydrogen peroxide chlorination unit was added dropwise to the flask. The temperature was then raised to 150°C for a sulfonation reaction over 4 hours, producing 20g of distilled acid. After sulfonation, the temperature was lowered to 100°C, and the distillation apparatus was shut off. 20g of distilled acid and 10g of water were added dropwise to initiate a hydrolysis reaction over 0.5 hours. After hydrolysis, the temperature was raised to 105°C, and 20g of a 30% formaldehyde aqueous solution was added dropwise to initiate a condensation reaction over 1 hour. After condensation, the temperature was lowered to 50°C, and 30% industrial sodium hydroxide alkali solution was added dropwise, ultimately yielding a coal-water slurry additive with a pH of 9 and a sulfonic acid group content of 16.4%.

[0049] Preparation of coal-water slurry: Take 81.1g of coal powder and 0.2g (dry basis) of the coal-water slurry additive prepared above, dilute with water to 100g, and stir evenly to obtain a flowable coal-water slurry. The flowability was tested according to the standard method and was B+. The apparent viscosity of the coal-water slurry at 25℃ was measured to be 878mPa·s using a viscometer, and the concentration of the coal-water slurry was measured to be 68.9wt% using a rapid moisture analyzer.

[0050] Example 4

[0051] 100g of styrene tar from a PO / SM unit was placed in a round-bottom flask equipped with a stirrer and distillation apparatus. The temperature was raised to 80°C, and 160g of 90% sulfuric acid from a hydrogen peroxide chlorination unit was added dropwise to the flask. The temperature was then raised to 160°C for a sulfonation reaction for 6 hours, producing 25g of distilled acid solution. After sulfonation, the temperature was lowered to 120°C, and the distillation apparatus was shut off. 25g of distilled acid solution was added dropwise to initiate a hydrolysis reaction for 1 hour. After hydrolysis, the temperature was lowered to 115°C, and 25g of 37% formaldehyde aqueous solution was added dropwise to initiate a condensation reaction for 1 hour. After condensation, the temperature was lowered to 40°C, and 32% industrial sodium hydroxide alkali solution was added dropwise, ultimately yielding a coal-water slurry additive with a pH of 8 and a sulfonic acid group content of 20.1%.

[0052] Preparation of coal-water slurry: Take 82.7g of coal powder and 0.2g (dry basis) of the coal-water slurry additive prepared above, dilute with water to 100g, and stir evenly to obtain a flowable coal-water slurry. The flowability was tested according to the standard method and was B+. The apparent viscosity of the coal-water slurry at 25℃ was measured to be 875mPa·s using a viscometer, and the concentration of the coal-water slurry was measured to be 70.3wt% using a rapid moisture analyzer.

[0053] Example 5

[0054] 100g of styrene tar from a PO / SM unit was placed in a round-bottom flask equipped with a stirrer and distillation apparatus. The temperature was raised to 80°C, and 150g of 70% sulfuric acid from a hydrogen peroxide chlorination unit was added dropwise to the flask. The temperature was then raised to 180°C for 5 hours of sulfonation, producing 22g of distilled acid. After sulfonation, the temperature was lowered to 150°C, and the distillation apparatus was shut off. 22g of distilled acid and 13g of water were added dropwise to initiate a 1.5-hour hydrolysis reaction. After hydrolysis, the temperature was lowered to 110°C, and 30g of 35% formaldehyde aqueous solution was added dropwise to initiate a 2-hour condensation reaction. After condensation, the temperature was lowered to 50°C, and 35% industrial sodium hydroxide alkali solution was added dropwise, ultimately yielding a coal-water slurry additive with a pH of 7 and a sulfonic acid group content of 15.3%.

[0055] Preparation of coal-water slurry: Take 80.8g of coal powder and 0.2g (dry basis) of the coal-water slurry additive prepared above, dilute with water to 100g, and stir evenly to obtain a flowable coal-water slurry. The flowability was tested according to the standard method and was rated as B. The apparent viscosity of the coal-water slurry at 25℃ was measured to be 885mPa·s using a viscometer, and the concentration of the coal-water slurry was measured to be 68.7wt% using a rapid moisture analyzer.

[0056] Comparative Example 1

[0057] 100g of styrene tar from a PO / SM unit was placed in a round-bottom flask equipped with a stirrer and distillation apparatus. The temperature was raised to 80°C, and 140g of 98% concentrated sulfuric acid was added dropwise to the flask. The temperature was then raised to 120°C for 2 hours of sulfonation, producing 20g of distilled acid. After sulfonation, the temperature was lowered to 140°C, and the distillation apparatus was shut off. 20g of distilled acid and 5g of water were added dropwise to initiate a 0.5-hour hydrolysis reaction. After hydrolysis, the temperature was lowered to 110°C, and 25g of 32% formaldehyde aqueous solution was added dropwise to initiate a 2-hour condensation reaction. After condensation, the temperature was lowered to 40°C, and 32% industrial sodium hydroxide alkali solution was added dropwise, ultimately yielding a coal-water slurry additive with a pH of 7 and a sulfonic acid group content of 12.5%.

[0058] Preparation of coal-water slurry: Take 80.7g of coal powder and 0.2g (dry basis) of the coal-water slurry additive prepared above, dilute with water to 100g, and stir evenly to obtain a flowable coal-water slurry. The flowability was tested according to the standard method and was B+. The apparent viscosity of the coal-water slurry at 25℃ was measured to be 876mPa·s using a viscometer, and the concentration of the coal-water slurry was measured to be 68.6wt% using a rapid moisture analyzer.

[0059] Comparative Example 2

[0060] 100g of raw naphthalene was placed in a round-bottom flask equipped with a stirrer and distillation apparatus. The temperature was raised to 80℃, and 160g of 90% sulfuric acid (from a hydrogen peroxide chlorination unit) was added dropwise to the flask. The temperature was then raised to 160℃ for 6 hours of sulfonation, producing 25g of distilled acid. After sulfonation, the temperature was lowered to 120℃, and the distillation apparatus was shut off. 25g of distilled acid was added dropwise to initiate a 1-hour hydrolysis reaction. After hydrolysis, the temperature was lowered to 115℃, and 25g of 37% formaldehyde aqueous solution was added dropwise to initiate a 1-hour condensation reaction. After condensation, the temperature was lowered to 40℃, and 32% industrial sodium hydroxide alkali solution was added dropwise, ultimately yielding a water-coal slurry additive with a pH of 8 and a sulfonic acid group content of 8.2%.

[0061] Preparation of coal-water slurry: Take 74.2g of coal powder and 0.2g (dry basis) of the coal-water slurry additive prepared above, dilute with water to 100g, and stir evenly to obtain a flowable coal-water slurry. The flowability was tested according to the standard method and was B+. The apparent viscosity of the coal-water slurry at 25℃ was measured to be 882mPa·s using a viscometer, and the concentration of the coal-water slurry was measured to be 63.1wt% using a rapid moisture analyzer.

[0062] Comparative Example 3

[0063] 100g of styrene tar from the PO / SM unit was placed in a round-bottom flask equipped with a stirrer and a total reflux device. The temperature was raised to 80℃, and 160g of 90% sulfuric acid from the chlorination-hydrogenation unit was added dropwise to the flask. The temperature was then raised to 160℃ for 6 hours of sulfonation. After sulfonation, the temperature was lowered to 120℃, and the total reflux device was shut off. After the hydrolysis reaction, the temperature was lowered to 115℃, and 25g of a 37% formaldehyde aqueous solution was added dropwise to initiate a condensation reaction for 1 hour. After the condensation reaction, the temperature was lowered to 40℃, and a 32% industrial sodium hydroxide solution was added dropwise, ultimately yielding a coal-water slurry additive with a pH of 8 and a sulfonic acid group content of 11.6%.

[0064] Preparation of coal-water slurry: Take 79.3g of coal powder and 0.2g (dry basis) of the coal-water slurry additive prepared above, dilute with water to 100g, and stir evenly to obtain a flowable coal-water slurry. The flowability was tested according to the standard method and was B+. The apparent viscosity of the coal-water slurry at 25℃ was measured to be 891mPa·s using a viscometer, and the concentration of the coal-water slurry was measured to be 67.4wt% using a rapid moisture analyzer.

[0065] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A method for preparing coal-water slurry additives using PO / SM tar, the method comprising: Using styrene tar as raw material, a high-efficiency coal-water slurry additive is obtained through a series of processes including sulfonation, hydrolysis, condensation, and neutralization. The styrene tar comes from a PO / SM unit, and its raw material composition is 60-80% styrene tricyclic and higher polymers, 10-20% diphenyl-butene, 1-10% 2,4-diethylphenyl-phenol, and 1-3% styrene. The sulfonation reaction is carried out in a reactor equipped with a distillation device. The sulfonating agent used in the sulfonation reaction is waste sulfuric acid produced by a hydrogen chloride-hydrochlorination unit, which contains 70wt% to 90wt% sulfuric acid. The hydrolysis agent used in the hydrolysis reaction is all the distilled acid produced during the sulfonation process and industrial water from the industrial park.

2. The method as described in claim 1, characterized in that, The condensation agent used in the condensation reaction is formaldehyde solution; and / or, the neutralizing agent used in the neutralization reaction is industrial sodium hydroxide or potassium hydroxide.

3. The method as described in claim 1, characterized in that, The mass ratio of styrene tar to waste sulfuric acid produced by the chlorination and hydrogenation unit is 1:1.4 to 1.6; and / or, the sulfonation reaction temperature is 120℃ to 180℃; the sulfonation reaction time is 2h to 6h; and / or, the mass ratio of distilled acid solution generated by the presence of azeotropic substances with water in the tar during the sulfonation reaction process to the raw material styrene tar is 0.2 to 0.25:

1.

4. The method according to any one of claims 1-3, characterized in that, The mass ratio of water to styrene tar in the hydrolysis reaction is 0.25 to 0.35:1; and / or the temperature of the hydrolysis reaction is 100°C to 150°C; and the time of the hydrolysis reaction is 0.5 h to 1.5 h.

5. The method according to any one of claims 1-3, characterized in that, In the condensation reaction, the mass ratio of formaldehyde solution to styrene is 0.2 to 0.3:1; and / or, the temperature of the condensation reaction is 105°C to 115°C; and the time of the condensation reaction is 1 hour to 2 hours.

6. The method according to any one of claims 1-3, characterized in that, The initial temperature of the neutralization reaction is 40℃~50℃; the neutralization reaction time is 1h~2h.

7. The coal-water slurry additive prepared by the method according to any one of claims 1-6.