Petroleum sulfonate supergravity neutralization process

Abstract

The present application relates to a kind of petroleum sulfonate supergravity neutralization process.The method mainly solves the problems of existing operation equipment, such as the corrosion of related pipeline, the blockage of process pipeline elbow, and the low content of product active substance.The method comprises the following steps: S1, the alkali solution is pumped into the supergravity reactor by self-alkali pump, and the liquid alkali is uniformly sprayed on the three-dimensional filler under the action of the distributor;S2, the sulfonic acid and the liquid of unsulfonated oil in the gas-liquid separator are pumped into the supergravity reactor by the sulfonic acid discharge pump;S3, the sulfonic acid and the liquid of unsulfonated oil are neutralized with the alkali solution on the filler of the supergravity reactor;S4, the product petroleum sulfonate generated by the neutralization reaction is pumped into the conditioning unit by the product discharge pump as part of the conditioning product, and part of the petroleum sulfonate is refluxed into the gas-liquid separator or the supergravity reactor.The petroleum sulfonate supergravity neutralization process can shorten the sulfonation and neutralization process, increase the content of product active substance, improve the fluidity of the material, and reduce corrosion and energy consumption.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of petroleum chemical industry, in particular to a petroleum sulfonate supergravity neutralization process. BACKGROUND

[0002] Petroleum sulfonate is a kind of extremely important oil displacement surfactant. In the petroleum sulfonate production process using gaseous sulfur trioxide as sulfonating agent and petroleum distillate oil as sulfonating raw material, there are some problems as follows: a large amount of sulfone anhydride and other impurity acid residues are produced when lubricating oil base oil is sulfonated with excessive sulfur trioxide, which are deposited, adhered and plugged in the material pipeline, and it is difficult to clean the coking substances and causes related pipeline corrosion and leakage; the current process flow often appears poor neutralization circulation during start-up and shutdown and reactor switching, which causes process interruption and makes it difficult to continuously produce, resulting in unplanned shutdown; the sulfonated product neutralization reaction is carried out in a high-speed shearing neutralization pump, and due to the particularity of petroleum sulfonate material, if the neutralization reaction is not timely, the viscosity will rapidly increase, causing poor discharge of the neutralization pump; if the reaction heat cannot be timely removed, the neutralization pump seal leakage is easily caused, increasing the workshop operation cost and environmental pollution; the current petroleum sulfonate active matter content index requirement is 38% (gravimetric method), and it is difficult to further improve the product active matter. SUMMARY

[0003] The present application is to overcome the problems of existing running equipment corrosion causing related pipeline plugging and low product active matter content in the background art, and provide a petroleum sulfonate supergravity neutralization process. The petroleum sulfonate supergravity neutralization process can shorten the sulfonation neutralization process flow, increase the product active matter content, improve the material fluidity, reduce corrosion and energy consumption, and prevent pipeline plugging.

[0004] The present application solves the problems by the following technical scheme: a petroleum sulfonate supergravity neutralization process, comprising the following steps:

[0005] S1, the alkali liquor is punched into the supergravity reactor from the alkali adding pump, and the liquid alkali is uniformly sprayed on the three-dimensional filler under the action of the distributor in the supergravity reactor;

[0006] S2, the sulfonic acid and the un-sulfonated oil liquid in the gas-liquid separator are punched into the supergravity reactor through the sulfonic acid discharge pump;

[0007] S3, the sulfonic acid and the un-sulfonated oil liquid are neutralized with the alkali liquor on the filler in the supergravity reactor;

[0008] S4, the product petroleum sulfonate generated by neutralization reaction is pumped by a neutralization circulating pump, part of which is used as a modulated product and enters a modulation unit by a product discharge pump; part of the petroleum sulfonate is refluxed into a gas-liquid separator or a supergravity reactor; the petroleum sulfonate refluxed into the gas-liquid separator by the neutralization circulating pump is pre-neutralized with the sulfonic acid generated by the reactor; and part of the petroleum sulfonate refluxed into the supergravity reactor is used to adjust the neutralization reaction intensity.

[0009] Preferably, when the neutralization reaction occurs on the packing of the supergravity reactor in step 3, the frequency of the motor of the supergravity reactor is adjusted to 30-50 Hz to adjust the residence time of the sulfonic acid and liquid alkali on the packing to 0.1-1 second, control the neutralization reaction time, and reduce the energy consumption of the petroleum sulfonate.

[0010] The neutralization reaction time is adjusted by frequency conversion of the supergravity reactor, which has certain influence on the flow performance of the product and the reflux ratio, and further reduces the energy consumption of the petroleum sulfonate. The petroleum sulfonate itself has large viscosity, and if the neutralization effect is not good, it is easy to cause pipeline blockage. Only when the neutralization reaction is sufficient and the mixing effect is good, the flow performance of the product can be improved to meet the process circulation reflux ratio.

[0011] Preferably, part of the petroleum sulfonate is refluxed into the gas-liquid separator by the neutralization circulating pump to be pre-neutralized with the sulfonic acid generated by the reactor; and part of the petroleum sulfonate is refluxed into the supergravity reactor to adjust the neutralization reaction intensity.

[0012] Preferably, the neutralization reaction conditions of the sulfonic acid and the non-sulfonated oil liquid with the alkali in the packing of the supergravity reactor are as follows: the mass percentage of the sulfonic acid and the non-sulfonated oil liquid to the alkali is 80-100:1; the supergravity rotation speed is 50-150 r / m; the material temperature is 60-90 ℃; and the reflux ratio is 5-10:1, and the reaction heat is taken away by the jacket circulating cooling water.

[0013] Preferably, the sulfonic acid and the non-sulfonated oil liquid in the gas-liquid separator are generated by the sulfonation reactor from the same direction of gaseous sulfur trioxide and liquid phase distillate oil.

[0014] Preferably, the sulfonation reactor is a membrane type or supergravity sulfonation reactor.

[0015] Preferably, the sulfonation reaction conditions are as follows: the molar ratio of gaseous sulfur trioxide to liquid phase distillate oil is 1.1-1.3:1, the volume concentration of sulfur trioxide gas is 2-7%, the temperature of sulfur trioxide gas is 50-80 ℃, and the temperature of the raw material oil is 50-80 ℃.

[0016] Preferably, the liquid phase distillate oil is a lubricating oil base oil, and the distillation range of the lubricating oil base oil is 200 ℃-400 ℃.

[0017] Preferably, the material sprayed on the surface of the packing is metal tantalum which is suitable for the neutralization reaction of the petroleum sulfonate.

[0018] Preferably, the alkali-adding pump is a multi-stage centrifugal pump.

[0019] Compared with the prior art, the present application has the following advantages:

[0020] The petroleum sulfonate supergravity neutralization process has the following advantages:

[0021] (1) Economic efficiency

[0022] Taking the 15000-ton petroleum sulfonate device of Daqing Refining and Chemical Company as an example, the supergravity neutralization process is realized, 10 tons of acid residue are saved per year, the cost is saved by about 350,000 yuan, the product is increased by 100,000 yuan, the flowability of the sulfonate product is enhanced, the neutralization cooler is cancelled, the steam consumption is saved by 10 tons, the operation and maintenance cost (labor cost and material cost) is reduced by 100,000 yuan, and the total is 550,000 yuan. The economic benefit is obvious.

[0023] (2) Efficiency

[0024] No need to invest in neutralization pump and neutralization cooler at one time and maintain, reduce unplanned shutdowns due to pipeline and equipment blockage, save time and labor cost.

[0025] (3) Reliability

[0026] In the supergravity device, the mass transfer and mixing of the material are greatly strengthened, the reaction is sufficient, the product is uniformly mixed, the flow performance is improved, and the stable operation of the device is guaranteed.

[0027] (4) Environmental protection

[0028] Reduce the discharge of hazardous waste, the index of the exhaust gas is stable, reduce the environmental pollution, and the social benefit is obvious.

[0029] The present application adopts the pre-neutralization and post-neutralization method, the first pre-neutralization is in the gas-liquid separator, and the second neutralization is in the supergravity. The petroleum sulfonate PH value of the reflux to the gas-liquid separator is controlled at 8-12, and the viscosity is relatively low. After mixing with the product from the sulfonation reactor, the flowability of the material in the gas-liquid separator is increased. The reflux position is below the liquid level of the gas-liquid separator, so that a part of the unsulfonated oil stays in the gas-liquid separator and continues to react with sulfur trioxide, which is called increasing the "aging time" in the industry, and the active material of the product can be increased by 1-10%.

[0030] The present application optimizes the two-phase feeding mode of the current supergravity reactor to a three-phase feeding mode, and adopts a three-dimensional layer design. The petroleum sulfonate mixing is more uniform, the flowability is better, and the process flow can run smoothly.

[0031] The packing rotor and liquid alkali distributor in the supergravity neutralization reactor of this invention are coated with tantalum metal, a special material suitable for the neutralization reaction of petroleum sulfonates, for the purpose of corrosion resistance. Attached Figure Description

[0032] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present invention and, together with the specification, serve to explain the technical solutions of the present invention.

[0033] Appendix Figure 1 This is a flowchart of the ultragravity neutralization process for petroleum sulfonates according to the present invention. Detailed Implementation

[0034] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0035] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments. Obviously, the obtained embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0036] This embodiment provides a petroleum sulfonate neutralization process using centrifugal force. Gas-phase sulfur trioxide and liquid distillate oil react in the same direction in a membrane or centrifugal sulfonation reactor to produce liquid sulfonic acid and a portion of unsulfonated oil, which enter a gas-liquid separator. The incompletely reacted sulfur trioxide tail gas flows to the tail gas treatment unit. The sulfonic acid and unsulfonated oil liquid are pumped into the centrifugal reactor via a sulfonic acid discharge pump, where they undergo a neutralization reaction with jet-type liquid sodium hydroxide from an alkali addition pump on the reactor packing. The neutralized petroleum sulfonate product is partially pumped into the conditioning unit as a conditioning product via a neutralization circulation pump, while the remaining petroleum sulfonate is returned to the gas-liquid separator or centrifugal reactor. The heat of reaction within the centrifugal reactor is carried away by jacketed circulating water.

[0037] like Figure 1 As shown, the petroleum sulfonate neutralization process of the present invention specifically includes the following steps:

[0038] Step 1: The alkali solution is pumped into the hypergravity reactor by a multi-stage centrifugal pump. Under the action of the distributor in the hypergravity reactor, the liquid alkali is sprayed evenly and under high pressure onto the three-dimensional packing.

[0039] Step 2: Gas-phase sulfur trioxide and liquid-phase distillate oil react in the same direction in a membrane or high-gravity sulfonation reactor to produce liquid sulfonic acid and some unsulfonated oil, which then enter the gas-liquid separator. The incompletely reacted sulfur trioxide tail gas flows to the tail gas treatment unit. The sulfonic acid and unsulfonated oil liquid are pumped into the high-gravity neutralization reactor via the sulfonic acid discharge pump.

[0040] The sulfonation reaction conditions are as follows: the molar ratio of gaseous sulfur trioxide to liquid distillate oil is 1.1-1.3:1, the volume concentration of sulfur trioxide gas is 2-7%, the temperature of sulfur trioxide gas is 50-80℃, and the temperature of the feed oil is 50-80℃. The liquid distillate oil is a lubricating oil base oil with a distillation range of 200℃ to 400℃.

[0041] Step 3: Sulfonic acid and unsulfonated oil liquid undergo a neutralization reaction with the alkali solution on the packing material of the centrifugal reactor. During the neutralization reaction, the frequency converter of the centrifugal reactor motor is adjusted to 30-50 Hz to regulate the residence time of sulfonic acid and liquid alkali on the packing material by 0.1-1 seconds, thereby controlling the neutralization reaction time and reducing the energy consumption of petroleum sulfonates. The packing material is coated with tantalum metal, which is suitable for the neutralization reaction of petroleum sulfonates.

[0042] The neutralization reaction conditions for sulfonic acid and unsulfonated oil liquid with alkali solution on the packing of a centrifugal reactor are as follows: mass percentage of sulfonic acid and unsulfonated oil liquid to alkali solution 80-100:1; centrifugal rotation speed 50-150 r / m; material temperature 60-90℃; reflux ratio 5-10:1; and the heat of reaction is carried away by the jacket circulating cooling water.

[0043] Step 4: The petroleum sulfonate product generated by the neutralization reaction is partially fed into the conditioning unit by the product discharge pump after passing through the neutralization circulation pump; the remaining petroleum sulfonate is returned to the gas-liquid separator or the high gravity reactor.

[0044] A portion of the petroleum sulfonates are refluxed into the gas-liquid separator via a neutralization circulation pump to undergo a pre-neutralization reaction with the sulfonic acid produced in the reactor; another portion of the petroleum sulfonates are refluxed into the hypergravity reactor to adjust the intensity of the neutralization reaction.

[0045] Example 1

[0046] The 60℃ liquid-phase petroleum distillate oil, serving as the base oil for lubricating oil with a distillation range of 200℃~400℃, enters the sulfonation reactor in parallel with the 65℃ gaseous sulfur trioxide to undergo a sulfonation reaction. The molar ratio of gaseous sulfur trioxide to liquid-phase distillate oil is 1.1-1.3:1, and the volume concentration of sulfur trioxide gas is 2-7%. The heat of the reaction is carried away by the circulating water in the reactor jacket. The liquid-phase sulfonic acid and the gaseous tail gas enter the gas-liquid separator. The 60-80℃ gas goes to the tail gas absorption and treatment unit, and the 60-100℃ liquid-phase sulfonate... The acid is pumped into a 150 rpm high-gravity reactor via a sulfonic acid discharge pump. Together with the refluxed petroleum sulfonate (reflux ratio 9:1), it is distributed along the centrifugal force direction onto the rotor packing. The rotating rotor packing elongates and thins the material, ensuring uniform distribution. Liquid alkali is pumped into the high-gravity reactor via a multi-stage centrifugal pump and sprayed onto the rotor packing via a distributor. The liquid alkali and sulfonic acid undergo a neutralization reaction inside the rotor packing. The liquid alkali flow rate is controlled by a regulating valve connected in series with an online product pH meter (pH 8-11). A neutralization circulation pump returns 45% of the reacted material to the gas-liquid separator, 45% to the high-gravity reactor, and 10% as a semi-finished product to the conditioning tank. The final product quality meets the following requirements: active ingredient content 40%, and interfacial tension between the 0.1%-0.3% concentration product and crude oil less than 1 x 10⁻⁶. -2 mN / m.

[0047] Example 2

[0048] The 60℃ liquid-phase petroleum distillate oil is used as the base oil for lubricating oil, with a distillation range of 200℃~400℃. It enters the sulfonation reactor in parallel with the 65℃ gaseous sulfur trioxide to undergo a sulfonation reaction. The heat of the reaction is carried away by the circulating water in the reactor jacket. The liquid-phase sulfonic acid and the gaseous tail gas enter the gas-liquid separator. The 60-80℃ gas goes to the tail gas absorption and treatment unit. The 60-100℃ liquid-phase sulfonic acid is pumped into the 120r / m high-gravity neutralization reactor by the sulfonic acid discharge pump. Together with the refluxed petroleum sulfonate (reflux ratio 9:1), it is distributed on the rotor packing along the centrifugal force direction. The material is elongated and thinned by the rotating rotor packing and is evenly distributed. The liquid alkali is pumped into the distributor in the high-gravity reactor by a multi-stage centrifugal pump and sprayed onto the high-gravity rotor packing. The liquid alkali and sulfonic acid undergo a neutralization reaction inside the rotor packing. The liquid alkali flow rate is connected in series with the online product pH meter (pH value 8-11) through a regulating valve. The neutralization circulation pump returns 90% of the reacted material to the gas-liquid separator, shutting off the return flow to the high-gravity reactor. The remaining 10% is pumped into the conditioning tank as a semi-finished product. The final product quality achieves: an active ingredient content of 39.8%, and an interfacial tension of less than 1 x 10⁻⁶ between the 0.1%-0.3% concentration product and crude oil. -2 mN / m.

[0049] The supergravity reactor used in this embodiment of the invention is manufactured by Huludao Tianhua Machinery Co., Ltd., and was developed and designed by Beijing University of Chemical Technology.

[0050] The petroleum sulfonate supergravity neutralization process of this invention reduces the discharge of solid waste acid slag, lowers energy consumption, and reduces unplanned shutdowns, thus reducing operating costs for enterprises. Taking the 15,000-ton petroleum sulfonate unit of Daqing Petrochemical Company as an example, the supergravity neutralization process saves 10 tons of acid slag annually (waste acid slag treatment fee of 3,500 yuan / ton), totaling 350,000 yuan; converts the slag into finished products, increasing profits by 100,000 yuan; enhances the fluidity of sulfonate products; eliminates the neutralization cooler, saving 10 tons of steam, totaling 2,000 yuan; and reduces unplanned shutdowns, lowering operation and maintenance costs (labor and material costs) by 100,000 yuan, totaling 552,000 yuan. This achieves the enterprise's goal of cost reduction and efficiency improvement, stabilizes exhaust gas indicators, reduces environmental pollution, and demonstrates significant social and economic benefits.

[0051] The above description represents only some embodiments of the present invention, but the present invention should not be limited to the content disclosed in these embodiments and accompanying drawings. Therefore, any equivalent or modified versions made without departing from the technical solutions disclosed in the present invention fall within the scope of protection of the present invention.

Claims

1. A process for neutralizing petroleum sulfonates under high gravity, characterized in that: Includes the following steps: The alkali solution is pumped into the hypergravity reactor by an alkali addition pump. Under the action of the distributor in the hypergravity reactor, the liquid alkali is sprayed evenly and under high pressure onto the three-dimensional packing. Sulfonic acid and unsulfonated oil liquid in the gas-liquid separator are pumped into the gravity reactor via the sulfonic acid discharge pump. Sulfonic acid and unsulfonated oil liquid undergo a neutralization reaction with alkaline solution on the packing material of a centrifugal reactor. The petroleum sulfonate product generated by the neutralization reaction is partially fed into the conditioning unit by the product discharge pump after passing through the neutralization circulation pump; the remaining petroleum sulfonate is returned to the gas-liquid separator or the centrifugal reactor. A portion of the petroleum sulfonates are refluxed into the gas-liquid separator via a neutralization circulation pump to undergo a pre-neutralization reaction with the sulfonic acid produced in the reactor; another portion of the petroleum sulfonates are refluxed into the hypergravity reactor to adjust the intensity of the neutralization reaction. The filler surface is coated with tantalum metal, which is suitable for the neutralization reaction of petroleum sulfonates.

2. The petroleum sulfonate neutralization process according to claim 1, characterized in that: When the neutralization reaction occurs on the packing material of the supergravity reactor, the frequency converter of the supergravity reactor motor is adjusted to 30-50 Hz to regulate the residence time of sulfonic acid and liquid alkali on the packing material by 0.1-1 seconds, thereby controlling the neutralization reaction time and reducing the energy consumption of petroleum sulfonates.

3. The petroleum sulfonate neutralization process according to claim 1, characterized in that: The neutralization reaction conditions for sulfonic acid and unsulfonated oil liquid with alkali solution on the packing of a centrifugal reactor are as follows: mass percentage of sulfonic acid and unsulfonated oil liquid to alkali solution 80-100:1; centrifugal rotation speed 50-150 r / m; material temperature 60-90℃; reflux ratio 5-10:1; and the heat of reaction is carried away by the jacket circulating cooling water.

4. The petroleum sulfonate neutralization process according to claim 1, characterized in that: The sulfonic acid and unsulfonated oil liquid in the gas-liquid separator are generated by the reaction of gaseous sulfur trioxide and liquid distillate oil in the same direction through the sulfonation reactor.

5. The petroleum sulfonate neutralization process according to claim 4, characterized in that: The sulfonation reactor is a membrane sulfonation reactor or a high-gravity sulfonation reactor.

6. The petroleum sulfonate neutralization process according to claim 4, characterized in that: The sulfonation reaction conditions are as follows: the molar ratio of gaseous sulfur trioxide to liquid distillate oil is 1.1-1.3:1, the volume concentration of sulfur trioxide gas is 2-7%, the temperature of sulfur trioxide gas is 50-80℃, and the temperature of feed oil is 50-80℃.

7. A petroleum sulfonate neutralization process under high gravity as described in claim 4 or 6, characterized in that: The liquid distillate oil is a lubricating oil base oil with a distillation range of 200℃ to 400℃.

8. The petroleum sulfonate neutralization process according to claim 1, characterized in that: The alkali addition pump is a multi-stage centrifugal pump.

Images