WO2016065662A1

WO2016065662A1 - Continuous petroleum sulfonate production method using micro-chemical technology

Info

Publication number: WO2016065662A1
Application number: PCT/CN2014/090450
Authority: WO
Inventors: 陈光文; 焦凤军
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2014-10-27
Filing date: 2014-11-06
Publication date: 2016-05-06
Also published as: CN105622468A

Abstract

A continuous petroleum sulfonate production method using micro-chemical technology, the method comprising: continuously passing a diluted petroleum fraction and diluted liquid sulfur trioxide through a micro-channel reactor combining a micro-reaction and micro heat exchange, and conducting reaction and heat-exchange in the micro-channel reactor to produce petroleum sulfonate; the resulting petroleum sulfonate flows out after being further cooled in a subsequent micro-channel heat exchanger, and enters a neutralization and salt-formation phase. The present invention is characterized in that the reactant sulfur trioxide is reacted with a petroleum fraction at a low mass ratio of 0.15~0.2, and the reaction equipment comprises a micro-channel reactor and a micro-channel heat exchanger, thus providing technical support for the continuous production of petroleum sulfonate on an industrial scale of tens of thousands of tons using micro-chemical technology.

Description

Method for continuously producing petroleum sulfonate by micro chemical technology

Technical field

The invention relates to a method for liquid phase SO ₃ sulfonated petroleum fraction, in particular to a method for continuously producing petroleum sulfonate by using micro chemical technology (that is, a method for continuously producing petroleum sulfonate by using a micro reactor).

Background technique

Oil is a first-level strategic resource related to national energy security, but current oil recovery is generally low. Petroleum sulfonate is considered to be the most promising surfactant for tertiary oil recovery due to its wide source of raw materials, strong interfacial activity, good compatibility with crude oil, good water solubility and low cost. Wide-distillate SO ₃ liquid phase sulfonation production of petroleum sulfonate is a rapid and strong exothermic reaction, and the existing process route mainly adopts a tank-type liquid phase continuous sulfonation method. The process is operated at a low temperature of 0 to 5 ° C, and the low temperature energy consumption is large. Due to the uneven micro-mixing in the reactor and the wide residence time of the material, the process uses a higher concentration of sulfonating agent; in addition, the heat of sulfonation reaction is derived from an external heat exchanger, and the local temperature is high and the mixing is uneven during the reaction. , resulting in unstable product quality.

CN101318112A describes the use of gravity and liquid SO ₃ sulfonation techniques for preparing flooding methods with anionic surfactants. At a reaction temperature of -10 to 50 ° C, a certain proportion of distillate is reacted with a sulfonating agent in a supergravity reactor, and at the same time, the reaction product is circulated in a circulating stirred tank and a supergravity reactor for 20 to 70 minutes. With an active content of more than 40%, the supergravity reactor enhances material mixing. However, there is material back-mixing in the process. The two modes of operation cannot solve the problem of rapid and original displacement of the sulfonation reaction heat, and the external circulation reflux reaction product method is used to remove part of the reaction heat.

Patent 201010206998 firstly discloses a microreactor technology for synthesizing petroleum sulfonate, and completes laboratory small-scale process development in a single microchannel reactor to achieve better results. However, when the process is applied for production amplification, in order to promote uniform distribution of materials in the microreactor, the reaction space velocity is 2.5-10 times that of the small test process. At this time, the heat exchange capacity in the single microreactor is insufficient, resulting in a partial reaction temperature. High, active content and the proportion of mono-disulfonate in the active material is slightly lower. Therefore, in the patent 201110397157, a staged sulfonation process is proposed, which disperses the heat of reaction in the two-stage microreactor and strengthens the original displacement heat to reduce the sulfonate. The reaction temperature is increased to increase the active concentration and the monosulfonic acid selectivity, and to increase the active tension characteristics. The concentration of the active substance in the above two patents is as high as 50%, and the concentration of the monosulfonate in the active material is 70±2%, and the active substance maintains the oil-water interfacial tension stably maintained at the level of ^10-2 mN·m ^-1 . Both patents are dedicated to adjusting product distribution by enhancing reaction heat transfer, but the reaction side has large thermal resistance, short reaction residence time, and limited heat transfer rate. To further improve the selectivity of monosulfonic acid, we control the temperature of the reaction raw material by lowering it. The reaction temperature rise (patent 201210122668.4), through the synergy with the original displacement heat, achieves effective control of the product structure, the monosulfonate concentration is higher than 75%.

In the production of 10,000-ton industrial-scale petroleum sulfonate, affected by the fluctuation of sulfur trioxide feed (containing acid slag), the micro-reaction system grading sulfonation process is difficult to operate stably without separate pump control equipment. The continuity of the reaction is tested. In addition, the pump equipment has a limited head. On the one hand, the raw material sulfur trioxide entrains the acid slag into the micro-reaction system, and on the other hand, although the reactant sulfonating agent and the raw material oil feed ratio are slightly higher, although the active substance concentration is high, There will be a lot less sulfonic acid formation, forming a product that is less soluble in the reaction system and deposited in the micro-reaction system. When operating for a long time, the system pressure drop will gradually increase until the flow rate is lower than the set load, which cannot satisfy the normal production.

Therefore, the continuous production of petroleum sulfonates by micro-chemical technology requires an updated process to adapt to existing production conditions.

Summary of the invention

To ensure that the microchannel reactor is used for the continuous production of 10,000 tons of petroleum sulfonate, the following technical methods are proposed.

The method comprises: continuously diluting the petroleum fraction and the diluted liquid sulfur trioxide through a microchannel reactor integrating microreaction and micro heat exchange, and reacting and heat exchange in the microchannel reactor to generate petroleum sulphur The acid and petroleum sulfonic acid are further cooled after cooling in a subsequent microchannel heat exchanger, and then enter the neutralization and salt formation section to form petroleum sulfonate. The main feature of the method is that the reactant sulfur trioxide and the petroleum fraction are reacted in a low mass ratio of 0.15 to 0.2; the heat of reaction is removed from the industrial circulating water to obtain a petroleum sulfonic acid having a temperature of 30 to 55 ° C; Another major feature of the process is that the reaction apparatus consists of only one of said microchannel reactors and a separate microchannel heat exchanger.

In the method of the present invention, the mass ratio of the sulfur trioxide to the petroleum fraction of the reactant refers to the ratio of the mass of pure sulfur trioxide in the diluted sulfonating agent to the mass of the pure distillate in the diluted petroleum fraction, that is, no dilution The mass of the agent or solvent, including the recovered dichloroethane. The mass concentrations of the reactant sulfur trioxide and the petroleum fraction after dilution are 20 to 30% and 50%, respectively (the same as the applicant's patents 201010206998.2, 201110397157.9). When the petroleum fraction is selected from a low boiling range fraction such as a diesel fraction, the reactant sulfur trioxide reacts with the petroleum fraction in a low mass ratio of 0.15 to 0.18, and when the petroleum fraction is selected from a high boiling range fraction such as a wax oil fraction, The reactant sulfur trioxide reacts with the petroleum fraction in a mass ratio of 0.18 to 0.2. The microchannel reactor integrates microreaction and micro-heat exchange, and the micro-reaction refers to micro-chemical unit operation in which the diluted petroleum fraction and the diluted liquid sulfur trioxide are micro-mixed and reacted; Heat refers to micro-chemical unit operations that perform in-situ heat exchange of micro-reacted materials including petroleum sulfonic acid. Micro-chemical unit operation micro-reaction and micro-heat exchange are carried out in a series of parallel interleaved micro-reaction channels and micro-heat exchange channels. These micro-reaction channels and micro-heat exchange channels constitute a micro-channel reactor, micro-reaction channels and micro-heat exchange The channels have any known size between equivalent diameters from 0.1 to 2.0 mm.

In the method of the present invention, a microchannel reactor and a microchannel heat exchanger constitute a microsystem for producing petroleum sulfonic acid, and the pressure drop of the microsystem is 0 to 0.5 MPa, preferably at a pressure drop of 0 to 0.2 MPa. . This parameter reduces the requirements on the feedstock pump while reducing power consumption.

In the method of the present invention, the diluent of the petroleum fraction and sulfur trioxide is dichloroethane, and the solvent dichloroethane can be recycled and reused. When the liquid sulfur trioxide raw material is diluted by the recovery solvent, the diluted liquid sulfur trioxide is pre-settling the acid slag before entering the microchannel reactor, and the acid slag precipitated by gravity is periodically discharged to the reaction section to neutralize the salt. The connecting pipe between the sections flows out along with the product petroleum sulfonic acid, enters the subsequent neutralization and salt formation section, and reacts the obtained petroleum sulfonic acid with ammonia water as a neutralizing agent, and the reaction is carried out in any existing known equipment. Such as titanium homogenizer.

Technical effect

The invention can obtain a higher petroleum sulfonic acid (salt) concentration and surface tension characteristic value of the product than the kettle reaction process under the ratio of the low reactant sulfur trioxide to the distillate feed, and at the same time, the amount of sulfur trioxide is higher than that of the kettle. The reaction process is reduced by 38.5-50% (based on the pot dosage of 0.325). The reduction of sulfur trioxide consumption greatly reduces the formation of inorganic salt by-products in the neutralization reaction section, providing a powerful process for subsequent processing and raw material cost control. Technical Support.

DRAWINGS

Figure 1. Microsystem apparatus and process, wherein: 1-microchannel reactor, 2-microchannel heat exchanger, 3-acid slag sedimentation separator; A-dilution oil, B-sulfonating agent, F1-flowmeter, F2-flowmeter, C1-cycle cooling water, C2-cycle cooling water backwater, P-de-neutralization section.

detailed description

The invention is specifically illustrated by the following non-limiting examples.

Equipment and Process: The following implementations were performed using the microsystem devices and processes shown in Figure 1. The microsystem unit consists of a microchannel reactor and a separate microchannel heat exchanger. The same as the microreactor or micro heat exchanger involved in the applicant's patent 201010206998 and patent 201110397157, on a scale scale, The microchannel reactor and the microchannel heat exchanger in the device were parallel-amplified, and two sets were switched in parallel. The microchannel reactor (1) in the device is composed of a series of parallel and micro-reaction channels and micro-heat exchange channels, and the micro-reaction channels and the micro-heat exchange channels respectively perform micro-reaction and micro-heat exchange respectively. The microreactor channel and the micro heat exchange channel have any known size between 0.1 and 2 mm in equivalent diameter; the microchannel reactor adopts a cross-flow reaction-heat exchange mode. The microchannel heat exchanger (2) involved in the device is an independent heat exchange device, and the main function is to further reduce the product temperature, and the microchannel heat exchanger adopts a countercurrent heat transfer form.

A separator (3) for sedimenting acid slag is pre-configured on the sulfur trioxide pipeline of the microsystem. The separator is designed with a central feed port, a top discharge port (clear liquid), and a bottom discharge port. Wherein, the middle feed port is a sulfur trioxide feed port, the top discharge port is connected to the microchannel reactor in the micro system device, and the bottom discharge port is connected to the product outlet pipe of the microchannel heat exchanger through a valve (reaction) The connecting pipe between the section and the neutralization salt section is shown in Figure 1). The lower part of the separator is designed as a tapered funnel. An inclined baffle is designed at the upper edge of the middle feed port to sediment the acid slag contained in the raw material sulfur trioxide to the bottom, and periodically discharge and neutralize the acid residue to prevent it from entering. Increase resistance within the equipment.

Process and operation: The pre-formulated sulfonating agent and petroleum distillate are used as raw materials, which are respectively transported by pipeline pump, and the flow rate is controlled by an industrial flowmeter, and then the micro-system is connected through a valve. Before cutting the two reaction materials into the micro-system device, the flow rate of the sulfonated oil is adjusted according to the design load of the micro-system. The sulfonation dosage is controlled according to the small range of the feed ratio of 0.15-0.2, and the two are firstly put into the kettle for a little time. After the flow is stably equilibrated, the sulfonated oil and sulfonating agent are separately switched to the microchannel reactor (MCR). The reaction heat transfer medium is circulating cooling water, because the micro heat exchange channel integrated in the microchannel reactor is micro-scale, and the channel in the microchannel heat exchanger is also micro-scale, and a filter is needed in the cooling water inlet pipe to remove water. The impurities avoid blocking the microchannel; the temperature of the circulating water of the circulating cooling water is determined by the utility. The invention requires that the temperature of the cooling water is 15 to 25 ° C and not more than 30 ° C to increase the heat transfer driving force (temperature difference). After the sulfonation reaction is completed in the microchannel reactor (MCR), the product then enters the microchannel heat exchanger (MCHE) for further heat exchange. The sulfonated product after heat exchange enters the product storage tank or goes to the neutralization section.

Sampling and analysis: The petroleum sulfonic acid was sampled at the bottom of the micro-system device outlet and the bottom-end tube of the kettle process, and the petroleum sulfonate and inorganic salt were formed in a 23% by mass aqueous ammonia solution at a pH of 8-10. Neutralize the end of the reaction. Neutralization samples were analyzed by active analysis, unsulfonated oil, inorganic salts and volatiles using a total analytical method (gravimetric method) for extraction separation and evaporation; chromatographic analysis of the ratio of active to non-sulfonated oil and single and double actives The concentration of polysulfonate; the interfacial tension of oil-water was measured by a rotary drop interface tension meter TX500C.

Example 1: Production of diesel as raw material

The diesel-based dilution oil with a mass concentration of 50% is used as the raw material, and the micro-system is debugged and operated under the flow load of 1000, 1200, 1400 kg/h of the raw material oil, and the flow rate of the raw material oil is controlled by the flow meter, and accordingly, the mass concentration is 25% of the sulfonating agent SO ₃ solution was controlled at a flow rate of 400 kg/h, 450 kg/h, and 450 kg/h, that is, the mass ratio of the sulfur trioxide to the petroleum fraction (SO ₃ /Oil) was 0.2, 0.19, and 0.16. . Under the above-mentioned feedstock oil load and reactant ratio, the first set of micro-system equipment was used, and the microchannel reactor in the apparatus had 1.25 mm equivalent parallel multi-channel, and the total resistance characteristic design value of the micro-system was 0.08 MPa/( 2000kg / h water). During the reaction, both the microchannel reactor and the microchannel heat exchanger use the factory circulating cooling water as the heat exchange medium, and the cooling water is connected to the reactor and the heat exchanger in parallel, and the flow rate does not interfere with each other, and the cooling water temperature is 24-28 °C. The reaction temperature measurement point is located on the connecting tube between the microchannel reactor and the microchannel heat exchanger, and the final discharge temperature measurement point is located on the microchannel heat exchanger outlet tube. The pressure drop measurement points of the microsystem include a diluent oil inlet and a sulfonate inlet, respectively located at the front end of the two inlet tubes of the microchannel reactor. Under the above various loads, a total of 120 hours of continuous operation, the flow rate of the reactant petroleum fraction and the measured SO ₃ /Oil mass ratio, and the micro system resistance, reaction temperature and discharge temperature are listed in Table 1, and the production operation results are as follows. Table 1 shows.

The obtained petroleum sulfonic acid enters the neutralization and salt formation section, and the petroleum sulfonate and inorganic salt are formed by the ammonia concentration of 23% by mass, and the pH value of the system is 8-10, which is the end point of the neutralization reaction.

In the process conditions shown in Table 1, the reaction temperature is significantly different from the tank reaction process (see Table 3 tank reaction process), reaching 50-60 ° C, the material temperature in the microchannel heat exchanger is higher than the discharge temperature, Above 40 °C. At this reaction temperature, the content of colloid in the diesel-based raw material is low, and the colloidal sulfonation product is not excessively produced, and the microchannel reactor can be stably operated for a long time.

In the results of the reaction shown in Table 1, the product was a volatile component in addition to the key components, including the solvent introduced by the raw material and the water brought in by the neutralization process. After deducting the solvent, the active concentration calculated from the active (oil sulfonate), unsulfonated oil and inorganic salt content reached 48.9 to 53.8%. And the concentration of monosulfonic acid reaches 79-85%, which is higher than the fractional sulfonation process and higher than the kettle production process. It is shown that at low SO ₃ /Oil feed mass ratios, the active content is not reduced and the monosulfonate is higher.

Table 1. Process conditions and operation results of continuous sulfonation of diesel in 120 hours

Example 2: Production of wax oil as raw material

The wax oil-based dilution oil with a concentration of 50% is operated under a load of 1200 kg/h through a flowmeter controlled flow rate, and a sulfonating agent SO ₃ solution having a concentration of 25 wt.% is controlled at a flow rate of 450 to 480 kg/h, that is, a reactant. The mass ratio of sulfur trioxide to petroleum fraction is from 0.19 to 0.2. The sulphonation of wax oil is directly switched, and the production of diesel sulphonation is uninterrupted. Affected by the fluidity of the wax oil, the microchannel reactor uses another set of equipment with a larger number of channels to reduce the flow resistance under the same load. The design of the resistance characteristic of the system is 0.05 MPa/(2000 kg/h water). Meanwhile, in order to lower the reaction temperature, in addition to lowering the cooling water inlet temperature to about 20 ° C, the feed quality ratio control of the reactant sulfur trioxide and the wax oil-based petroleum fraction is equivalent to that of the diesel-based raw material production process, that is, the above 0.19~ 0.2. The 55-hour continuous operation data of the petroleum oil sulfonate produced by the wax-based feedstock oil is shown in Table 2.

In the operation data shown in Table 2, the flow rate of the wax-based feedstock oil solution is decreasing, mainly because the flow rate of the sulfonating agent is periodically fluctuated (determined by the production process conditions), resulting in a gradual increase in temperature during the sulfonation of the wax oil, thereby The sulfonated component of the wax oil is sulfonated and the resistance of the microsystem is increased. The fluctuation of the sulfonating agent is mainly due to its high viscosity acid residue, which has a negative effect on the continuous production using micro-chemical technology. Therefore, the present invention proposes pretreatment of the sulfonating agent feed, that is, pretreatment of the settled acid slag so that a very small amount of acid slag contained therein does not enter the micro system.

Table 1 and Table 2 show that the pressure of the diesel sulfonation system is lower than that of the wax oil sulfonation system, and the stability is better than the wax oil reaction system; the temperature of the diesel sulfonation reaction can be controlled at 50-60 ° C, while the wax oil is sulfonated. The reaction temperature is then 60-70 ° C. The concentration of unsulfonated oil in the sulfonated product of wax oil is higher, and more reactants are still not sulfonated. According to the present invention, the SO ₃ consumption of the sulfonated reactant is reduced, and the saved SO ₃ can continue to be used for the resulfonation production of the unsulfonated oil.

Table 2. Process conditions and operation results of continuous sulfonation of wax oil-based feedstock oil to produce petroleum sulfonate

Comparative Example 1: Production of petroleum sulfonate from diesel and wax oil in a kettle process

The kettle process and the microchemical process use the same concentration of feedstock oil and sulfonating agent. In the kettle process, the reactant feed ratio of the diesel-based diluent oil to the raw material is 0.3, and the reactant feed ratio of the wax-based diluent oil as the raw material is 0.33, and the reaction heat is removed by the cold-cold brine. The product composition of the process was sampled and analyzed and is listed in Table 3.

Comparing the operating data of the comparative example and the comparative example, the active concentration of the product and the selectivity of the monosulfonic acid in the present invention are higher than the state of the art at a lower reactant feed ratio, wherein the active concentration of the product using diesel as a raw material The selectivity to monosulfonic acid is better than that of the kettle process.

Table 3. Results of sulfonation operation of kettle type process oil and wax oil

The invention provides technical guarantee for the micro chemical technology to be used for the continuous production of 10,000-ton industrial scale petroleum sulfonate.

Claims

A method for continuously producing petroleum sulfonate by micro-chemical technology, characterized in that a diluted liquid sulfur trioxide and a diluted petroleum fraction are continuously passed through a microchannel reactor and reacted at a low mass ratio in a microchannel reactor. The petroleum sulfonic acid is formed, and the obtained petroleum sulfonic acid is further cooled after being cooled in a subsequent microchannel heat exchanger, and the petroleum sulfonate is obtained by neutralizing the salt forming section.
The method according to claim 1, wherein the low mass ratio means a ratio of said liquid sulfur trioxide to a petroleum fraction having a value of from 0.15 to 0.2.
The method according to claim 1, wherein said microchannel reactor integrates microreaction and microheat exchange, and microreaction refers to micromixing said diluted petroleum fraction and diluted liquid sulfur trioxide, and The micro-chemical unit operation in which the reaction takes place; the micro-heat exchange refers to the operation of the micro-chemical unit for in-situ heat exchange of the material obtained by micro-reaction including petroleum sulfonic acid.
The method according to claim 3, wherein the micro-chemical unit operates the micro-reaction and the micro-heat exchange in a series of parallel interleaved micro-reaction channels and micro-heat exchange channels; the micro-reaction channels and the micro-heat exchange channels constitute the The microchannel reactor has an arbitrary size of any equivalent diameter between 0.1 and 2 mm.
The method of claim 1 wherein the petroleum sulfonic acid-producing system consisting of a microchannel reactor and a microchannel heat exchanger has an operating pressure drop of from 0 to 0.5 MPa.
The method according to claim 1, wherein the diluent of the petroleum fraction and the liquid sulfur trioxide is dichloroethane, and the dichloroethane is recyclable; when the sulfur trioxide is diluted with the recovered solvent dichloroethane, The diluted liquid sulfur trioxide is pre-settling the acid slag before entering the microchannel reactor, and the settled acid slag is periodically discharged directly into the petroleum sulfonic acid material flowing out of the microchannel heat exchanger, and neutralized with petroleum sulfonic acid. Salt section.
The method according to claim 1 or 6, wherein the diluted petroleum fraction and the diluted liquid sulfur trioxide have a mass concentration of 50% and 20 to 30%, respectively.
The method of claim 1 wherein the neutralizing salt forming section reacts with petroleum sulfonic acid with ammonia as a neutralizing agent, and the reaction is carried out in any of the existing known apparatus.