CN115584284A - Continuous catalytic oxidation-free Fischer-Tropsch wax system and method - Google Patents
Continuous catalytic oxidation-free Fischer-Tropsch wax system and method Download PDFInfo
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Abstract
The invention discloses a continuous catalytic oxidation-free Fischer-Tropsch wax system and a method. Wherein, this system includes: the raw material unit comprises a Fischer-Tropsch wax storage tank and an auxiliary agent storage tank, and heating equipment for heating a solid-phase raw material into a liquid-phase raw material is arranged outside the Fischer-Tropsch wax storage tank and the auxiliary agent storage tank; the staged oxidation unit comprises at least two stages of oxidation reactors connected in series, a gas-liquid separator for performing gas-liquid separation on the effluent of the oxidation reactor is arranged at the downstream of each stage of oxidation reactor, and the first stage of oxidation reactor is communicated with the Fischer-Tropsch wax storage tank and the auxiliary agent storage tank through pipelines; and the tail gas treatment unit is communicated with the gas-phase outlets of the gas-liquid separators of all stages. By applying the technical scheme of the invention, the solid-phase raw material preheating device is arranged to preheat the solid-phase raw material in advance, so that the temperature of the solid-phase raw material with lower temperature can be reduced, the temperature of the liquid-phase raw material in the liquid-phase circulation loop can be reduced, the possibility of continuous non-catalytic oxidation time increase caused by the temperature reduction of the reflux liquid-phase raw material can be avoided, and the reaction efficiency can be further improved.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a continuous catalytic oxidation-free Fischer-Tropsch wax system and a method.
Background
The Fischer-Tropsch wax can be widely used in the fields of food cosmetics, printing ink and coatings, rubber and plastic processing, hot melt adhesives, investment casting and the like, and can be used as a modifier of paraffin and microcrystalline wax to improve the dropping point and hardness of the Fischer-Tropsch wax because the Fischer-Tropsch wax is easy to be mutually soluble in petroleum wax, microcrystalline wax, polyolefin and the like. The Fischer-Tropsch wax can replace the traditional paraffin to prepare the oxidized wax, relieve the pressure of shortage of petroleum resources and improve the economic added value of the coal-based wax by benefiting from a plurality of advantages of the Fischer-Tropsch wax. Since the Fischer-Tropsch wax is a non-polar molecule, the properties of the Fischer-Tropsch wax can be improved by introducing a polar molecule into the Fischer-Tropsch wax through a chemical method, and a wider application space is searched for. The oxidation modification of the Fischer-Tropsch wax is a process of introducing polar groups such as-OH, -COOH, -CHO, -COC-, -COOR and the like by a chemical method, so that the aspects of the Fischer-Tropsch wax, such as affinity, emulsibility, solubility, lubricity, pigment dispersibility and the like, are fundamentally improved.
At present, the catalytic oxidation method/non-catalytic oxidation method is mainly adopted in China to prepare oxidized wax products. In the process of preparing oxidized wax by a catalytic oxidation method, catalysts used for wax oxidation are mainly manganese soap and cobalt soap catalysts, and the catalysts are matched with oxygen-containing gases such as air, oxygen and the like to produce the oxidized wax. The method has the disadvantages that by-products are obviously increased in the wax oxidation process along with the excessive introduction of the catalyst, the color and luster of the oxidized wax are influenced by the residual metal ions, and the produced oxidized wax has poor quality, is mainly reflected in deep color and heavy smell, and cannot be applied to the daily chemical industry. For example, CN103468316A uses manganese acetate and manganese sulfate as catalysts, stearic acid as an auxiliary agent, paraffin and microcrystalline wax are oxidized under the action of oxygen, but in the process of oxidation reaction, manganese acetate or manganese sulfate is separated out and cannot be well dissolved in wax to participate in catalytic reaction, and the color and smell of the product are also affected. In order to eliminate the influence of residual metal ions on the product quality, researchers have made various improvements on the catalytic oxidation method. CN102921447A designs Co/SBA-15 immobilized catalyst to carry out oxidation modification on paraffin, although SBA-15 molecular sieve is used as carrier to anchor catalytic active component, the specific surface area of the catalyst is improved, the macroporous structure of the catalyst is enriched, but the catalytic activity of the catalyst still needs to be further improved because the active site of the catalyst mainly consists of cobalt oxide. In addition, the introduction of solid phase catalyst can increase the cost of practical application, and no mature process and equipment exist at present. A non-catalytic oxidation method of wax is also reported, CN105087068A oxidizes Fischer-Tropsch coal to prepare wax by means of oxygen and an initiator under the condition of no catalyst, although the process does not adopt a transition metal ion catalyst, the color and smell of a product are not influenced, a device used for oxidation reaction is a three-mouth bottle, oxygen cannot be uniformly contacted with molten Fischer-Tropsch wax, the dispersion degree of the oxygen in an oxidation device is poor, and therefore, the acid value and the saponification value of the product still have a space for further improving. In addition, the oxygen used in the oxidation reaction has a greater risk of bringing Volatile Substances (VOCs) in the tail gas into contact with oxygen to the explosive limit, and thus this design is not conducive to large-scale development, production, and application.
Although the air has weaker oxidizing power than strong oxidizing power gases such as oxygen, ozone and the like, the mildness is more favorable for industrial application. CN 113797867A adopts continuous microchannel reaction technology to prepare the oxidized coal-based Fischer-Tropsch wax under the action of air. Although the process can greatly improve the mass transfer efficiency, improve the heterogeneous reaction mixing efficiency of the Fischer-Tropsch wax-oxygen-containing gas and shorten the reaction time, the micro-scale channel size and the very complex internal structure of the microreactor make the channel of the reactor easily blocked after the wax is solidified, and the cleaning becomes very difficult. In addition, the micro-reactor adopts 'number increasing amplification' to enlarge the capacity, and although the amplification cost can be effectively reduced, the processing capacity is also greatly limited. As the number of microreactors increases, the complexity of monitoring and controlling the microreactors increases, and the operating costs for practical production increase. The existing technology for preparing oxidized wax is mostly carried out by adopting a single small-sized air-entrapping bubbling reaction kettle type device, and the flow rate, specific consumption and dispersity of air can all influence the wax oxidation depth. And the feeding, discharging and oxidizing processes are operated in batch-wise manner, after the oxidizing process of a batch of wax is completed, the oxidizing process needs to be stopped, the prepared oxidized wax is discharged from the reaction kettle, and then the feeding is carried out again for the next round of oxidation. Although such a batch process has low requirements for equipment, the process still has room for improvement for industrial application.
Disclosure of Invention
The invention aims to provide a continuous catalytic-free Fischer-Tropsch wax oxidation system and a continuous catalytic-free Fischer-Tropsch wax oxidation method, so that oxidation reaction can be carried out in a short time, and the quality of an obtained oxidation product is greatly improved.
To achieve the above objects, according to one aspect of the present invention, there is provided a continuous non-catalytic oxidation fischer-tropsch wax system. The continuous catalytic oxidation-free Fischer-Tropsch wax system comprises: the raw material unit comprises a Fischer-Tropsch wax storage tank and an auxiliary agent storage tank, and heating equipment for heating a solid-phase raw material into a liquid-phase raw material is arranged outside the Fischer-Tropsch wax storage tank and the auxiliary agent storage tank; the graded oxidation unit comprises at least two stages of oxidation reactors connected in series, a gas-liquid separator for performing gas-liquid separation on effluent of each stage of oxidation reactor is arranged at the downstream of each stage of oxidation reactor, and the first stage of oxidation reactor is communicated with the Fischer-Tropsch wax storage tank and the auxiliary agent storage tank through pipelines; and the tail gas treatment unit is communicated with the gas-phase outlets of the gas-liquid separators of all stages.
Furthermore, the oxidation reactor is an oxidation reactor with 2-3 stages connected in series.
Furthermore, a filter for filtering impurity metals in the liquid phase raw materials is arranged between the Fischer-Tropsch wax storage tank and the oxidation reactor.
Further, the lower part of the oxidation reactor is provided with a liquid-phase feed inlet and an air inlet, and the top of the oxidation reactor is provided with an outlet material; the discharge hole of the first stage oxidation reactor is communicated with the first stage gas-liquid separator through a pipeline, the liquid phase outlet of the first stage gas-liquid separator is communicated with the liquid phase feed inlet of the next stage oxidation reactor through a pipeline, and the liquid phase outlet of the last stage oxidation reactor is communicated with the finished product box.
Further, an inorganic membrane gas distribution device for uniformly dispersing air in the oxidation reactor is arranged at an air inlet of the oxidation reactor; preferably, the pore size of the inorganic membrane in the inorganic membrane gas distribution device is 0.3 to 2.0. Mu.m, preferably 0.3 to 1.0. Mu.m.
Further, the tail gas treatment unit comprises a water washing tower, an oil-water separator and a circulating water pipeline which are communicated.
According to another aspect of the invention, there is provided a process for the continuous non-catalytic oxidation of a fischer-tropsch wax. The method comprises the following steps: respectively preheating and melting Fischer-Tropsch wax and an auxiliary agent, mixing the molten Fischer-Tropsch wax and the auxiliary agent as liquid-phase raw materials, and introducing the liquid-phase raw materials into at least two stages of oxidation reactors connected in series for a non-catalytic oxidation reaction; after gas-liquid separation, the oxidation reaction effluent of the first stage oxidation reactor enters the next stage oxidation reactor to continuously carry out non-catalytic oxidation reaction until the reaction of the last stage oxidation reactor is finished, a liquid phase product is discharged as an oxidized wax product, and the gas phase of the effluent of each stage oxidation reactor after gas-liquid separation is washed by water and discharged.
Furthermore, the oxidation reactor is a 2-3-stage oxidation reactor connected in series; preferably, when the liquid phase raw materials are mixed and introduced into the at least two stages of oxidation reactors connected in series, air is introduced into the oxidation reactors and is dispersed into the liquid phase raw materials through the inorganic membrane gas distribution device; more preferably, the flow rate of air is 6.6 to 33.3mL/min g, preferably 13.33 to 20mL/min g; wherein the flow rate represents the flow rate relative to 1g of Fischer-Tropsch wax air; more preferably, the pore size of the inorganic membrane in the inorganic membrane gas distribution device is 0.3 to 2.0. Mu.m, preferably 0.3 to 1.0. Mu.m.
Further, the Fischer-Tropsch wax is at least one selected from the group consisting of 52#, 60#, 70#, 80#, 90#, 105#, 110# and 115# Fischer-Tropsch wax; the auxiliary agent is one or more of stearic acid, glacial acetic acid, citric acid and oxidized Fischer-Tropsch wax.
Further, the temperature of the non-catalytic oxidation reaction is 120-180 ℃, preferably 150-170 ℃; the time of non-catalytic oxidation is 1 to 4 hours, preferably 1.5 to 3 hours; preferably, the preheating melting temperature is 100 to 180 ℃.
By applying the technical scheme of the invention, the solid-phase raw material preheating device is arranged to preheat the solid-phase raw material in advance, so that the temperature of the solid-phase raw material with lower temperature can be reduced, the temperature of the liquid-phase raw material in the liquid-phase circulation loop can be reduced, the possibility of increasing the continuous non-catalytic oxidation time caused by the temperature reduction of the reflux liquid-phase raw material is avoided, and the reaction efficiency is further improved. Therefore, even if the liquid-phase component flowing from the upper oxidation reactor to the lower oxidation reactor contains a newly added liquid-phase raw material which has not reacted for a sufficient time, the liquid-phase raw material can continue the oxidation reaction in the lower oxidation reactor to achieve a sufficient degree of oxidation. The wax oxidation process can be continuously carried out without stopping the oxidation process midway, and the production efficiency is greatly improved. In addition, because wax oxidation is exothermic reaction, the oxidation reactor does not need to be additionally provided with a heating device in the continuous oxidation process, and the production cost is reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
figure 1 shows a schematic flow diagram for the continuous non-catalytic oxidation of fischer-tropsch wax according to an embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Aiming at the technical problems recorded in the background technology, the invention provides the following technical scheme to realize the oxidation reaction in a short time and greatly improve the quality of the obtained oxidation product.
According to an exemplary embodiment of the present invention, a continuous non-catalytic oxidation Fischer-Tropsch wax system is provided. The continuous catalytic oxidation-free Fischer-Tropsch wax system comprises: the raw material unit comprises a Fischer-Tropsch wax storage tank and an auxiliary agent storage tank, and heating equipment for heating a solid-phase raw material into a liquid-phase raw material is arranged outside the Fischer-Tropsch wax storage tank and the auxiliary agent storage tank; the staged oxidation unit comprises at least two stages of oxidation reactors connected in series, a gas-liquid separator for performing gas-liquid separation on the effluent of the oxidation reactor is arranged at the downstream of each stage of oxidation reactor, and the first stage of oxidation reactor is communicated with the Fischer-Tropsch wax storage tank and the auxiliary agent storage tank through pipelines; and the tail gas treatment unit is communicated with the gas-phase outlets of the gas-liquid separators of all stages.
By applying the technical scheme of the invention, the solid-phase raw material preheating device is arranged to preheat the solid-phase raw material in advance, so that the temperature of the solid-phase raw material with lower temperature can be reduced, the temperature of the liquid-phase raw material in the liquid-phase circulation loop can be reduced, the possibility of increasing the continuous non-catalytic oxidation time caused by the temperature reduction of the reflux liquid-phase raw material is avoided, and the reaction efficiency is further improved. Therefore, even if the liquid-phase component flowing from the upper oxidation reactor to the lower oxidation reactor contains a newly added liquid-phase raw material which has not reacted for a sufficient time, the liquid-phase raw material can continue the oxidation reaction in the lower oxidation reactor to achieve a sufficient degree of oxidation. Preferably, the preheating melting temperature is 100-180 ℃. The wax oxidation process can be continuously carried out without stopping the oxidation process midway, and the production efficiency is greatly improved. In addition, the wax oxidation is an exothermic reaction, so that an oxidation reactor does not need to be additionally provided with a heating device in the continuous oxidation process, and the production cost is reduced.
In order to sufficiently and efficiently react the raw materials, the oxidation reactor is preferably 2 to 3 oxidation reactors connected in series, and more preferably, a liquid-phase circulation circuit is provided for each oxidation reactor. And a filter for filtering impurity metals in the liquid-phase raw materials is arranged among the Fischer-Tropsch wax storage tank, the auxiliary agent storage tank and the oxidation reactor so as to improve the purity of the product.
In one embodiment of the invention, the lower part of the oxidation reactor is provided with a liquid-phase feed inlet and an air inlet, and the top of the oxidation reactor is provided with an outlet material; the discharge port of the first stage oxidation reactor is communicated with the first stage gas-liquid separator through a pipeline, the liquid phase outlet of the first stage gas-liquid separator is communicated with the liquid phase feed port of the next stage oxidation reactor through a pipeline, and the liquid phase outlet of the last stage oxidation reactor is communicated with the finished product box.
In a typical embodiment of the present invention, the inorganic membrane gas distribution device with smaller pore size makes the air bubbles generated in the liquid phase raw material smaller, improves the dispersion degree of the air in the liquid phase raw material, enhances the contact efficiency of the gas-liquid two phases, improves the depth of the oxidation reaction, and further accelerates the reaction process. Preferably, the pore size of the inorganic membrane in the inorganic membrane gas distribution device is 0.3 to 2.0. Mu.m, preferably 0.3 to 1.0. Mu.m.
Preferably, the tail gas treatment unit comprises a water washing tower, an oil-water separator and a circulating water pipeline which are communicated. Gas in the gas-liquid separator enters a water washing tower to be cooled to 0-25 ℃, and the gas is safely discharged through an oil-water separator, so that green production is realized.
According to a typical embodiment of the present invention, a process for the continuous non-catalytic oxidation of a fischer-tropsch wax. The method comprises the following steps: respectively preheating and melting Fischer-Tropsch wax and an auxiliary agent, mixing the molten Fischer-Tropsch wax and the auxiliary agent as liquid-phase raw materials, and introducing the liquid-phase raw materials into at least two stages of oxidation reactors connected in series for a non-catalytic oxidation reaction; after gas-liquid separation, the oxidation reaction effluent of the first stage oxidation reactor enters the next stage oxidation reactor to continuously carry out non-catalytic oxidation reaction until the reaction of the last stage oxidation reactor is finished, a liquid phase product is discharged as an oxidized wax product, and the gas phase of the effluent of each stage oxidation reactor after gas-liquid separation is washed by water and discharged.
According to a typical embodiment of the present invention, the flow rate of air is 6.6 to 33.3mL/min g, preferably 13.33 to 20mL/min g; wherein the flow rate represents the flow rate relative to 1g of Fischer-Tropsch wax air; by adopting the technical scheme of the invention, the flow of air can be controlled on the premise of ensuring the oxidation degree, color, target product selectivity and ester-acid ratio of the product, so that the total amount of air introduced into the reaction system achieves the optimal effect, the reaction time is shortened, the oxidation degree of the product is improved, and the lowest cost is ensured. Preferably, the temperature of the non-catalytic oxidation reaction is 120-180 ℃, preferably 150-170 ℃ (the reaction temperature of each level is consistent); the time without catalytic oxidation is 1 to 4 hours, preferably 1.5 to 3 hours. By adopting the preferable conditions, under the simultaneous action of higher air flow and higher oxidation temperature, water generated after the esterification reaction of the fatty acid in the by-product and the alcohol substance is quickly taken out from the reactor in the form of steam, which is more beneficial to the forward progress of the esterification reaction and promotes the generation of the ester substance.
In the present invention, the fischer-tropsch wax may be at least one selected from the group consisting of 52#, 60#, 70#, 80#, 90#, 105#, 110#, and 115# fischer-tropsch wax; wherein, the 60# Fischer-Tropsch wax means that the melting point of the Fischer-Tropsch wax is 60 ℃, and the other same reasons are carried out. The auxiliary agent is one or more of stearic acid, glacial acetic acid, citric acid and oxidized Fischer-Tropsch wax, and stearic acid is preferred. These adjuvants can deepen the degree of oxidation and further increase the acid number and saponification number of the oxidized wax.
Compared with the prior art, the Fischer-Tropsch wax oxidation method can realize oxidation reaction in a short time, and the quality of the obtained oxidation product is greatly improved. The ester value of the oxidized wax is 50-200 mgKOH/g; the acid value is 20-80 mgKOH/g; the ratio of ester to acid is > 1, preferably 1.2 to 3.2. The tail gas generated in the oxidation process can be safely discharged, the obtained product has light color and no pungent smell, and the requirements of wax products in the application fields of emulsibility, oil solubility, lubricity, pigment dispersibility and the like are completely met.
In one embodiment of the invention, as shown in FIG. 1, 1-raw material storage tank and auxiliary agent storage tank, 2-filter, 3-air compressor, 4-flowmeter I, 5-primary oxidation reactor, 6-primary gas-liquid separation tank, 7-secondary oxidation reactor, 8-flowmeter II, 9-secondary gas-liquid separation tank II, 10-water scrubber, 11-finished product tank, 12-oil-water separator. The continuous catalytic-free oxidation method of Fischer-Tropsch wax is realized by the following steps: solid phase raw materials in a raw material storage tank and an auxiliary agent storage tank 1 are preheated and converted into liquid phase raw materials, the liquid phase raw materials pass through a filter 2 and then enter a primary oxidation reactor 5 for reaction through a gear pump, air enters the primary oxidation reactor 5 from an air compressor through a flow meter I, then products of the primary oxidation reactor 5 enter a primary gas-liquid separation tank 6 to realize the separation of gas and liquid, the gas enters a washing tower, liquid phase reactants continue to enter a secondary oxidation reactor 7 for reaction, the air enters the secondary oxidation reactor 7 from the air compressor through a flow meter II, then products of the secondary oxidation reactor 7 enter a secondary gas-liquid separation tank 9 to realize the separation of the gas and the liquid, the liquid phase products enter a finished product box 11, and the gas in the secondary gas-liquid separation tank 9 and the gas in the washing tower 10 together enter a circulating water pump 6 and are washed by circulating water and then pass through an oil-water separator 12 to realize the safe discharge of the gas. Wherein, the air is supplied by an air compressor, the air compressor is connected with an air inlet through a pipeline, and a flowmeter is fixedly arranged on the pipeline to adjust the air flow required by the oxidation process.
The following examples are provided to further illustrate the advantageous effects of the present invention.
The acid number represents the number of milligrams of potassium hydroxide required to neutralize 1g of chemical, in mg. KOH/g;
the saponification value represents the number of milligrams of potassium hydroxide consumed by 1g of chemical substance hydrolyzed in alkali, in mg. KOH/g;
the ester value = saponification value-acid value in mg · KOH/g;
the ratio of ester acids = ester value/acid value.
Raw material 1:105# Fischer-Tropsch wax, which has a freezing point of 99 ℃, a drop melting point of 106.4 ℃, an oil content of less than or equal to 0.5 percent and a penetration degree of 3/0.1mm, and is purchased from Fischer-Tropsch wax A of which the model is FR100 and which is sold by Huangjiang Huangxing chemical industry Co., ltd;
raw material 2:100# Fischer-Tropsch wax, with a congealing point of 89.5 ℃, a drop melting point of 98.7 ℃, an oil content of 0.2 percent and a penetration of 5/0.1mm, was purchased from Fischer-Tropsch wax A of model FR90 sold by Huangjiang chemical industries, ltd.
Raw material 3:60# Fischer-Tropsch wax, freezing point of 56.7 ℃, drop melting point of 60.4 ℃, oil content of 1.33 percent, penetration of 0.9/0.1mm, cut from Ningpo coal and hydrorefined bottom oil.
Examples 1 to 3
Referring to the flow of fig. 1, fischer-tropsch wax and 3% stearic acid are preheated in a storage tank, then enter a primary oxidation reactor, are gradually heated to 120 ℃ to be completely melted, then enter the primary oxidation reactor from an air compressor through a flowmeter, and are introduced with air at the flow rate of 16.6mL/min g for catalytic oxidation. Under the action of the gear pump, the liquid-phase reactant enters a secondary oxidation reactor and continues catalytic oxidation with the introduced air. Wherein the aperture of the inorganic membrane reaction devices in the first-stage oxidation reactor and the second-stage oxidation reactor is 0.5um, the reaction temperature is 170 ℃, and the reaction time is 3 hours, so that the oxidized wax A1-A3 is obtained.
The acid number, saponification number, ester number and ester-to-acid ratio of the oxidized waxes A1 to A3 were as shown in Table 1.
TABLE 1 Performance parameters of the oxidized waxes A1 to A3
| Acid value (mgKOH/g) | Soap value (mgKOH/g) | Ratio of ester to acid | |
| Example 1 (starting Material 1) | 27.11 | 66.50 | 1.65 |
| Example 2 (starting Material 2) | 39.21 | 92.37 | 1.35 |
| Example 3 (starting material 3) | 40.03 | 94.92 | 1.37 |
Examples 4 to 6
Preheating Fischer-Tropsch wax and 3% of stearic acid in a storage tank, then feeding the preheated Fischer-Tropsch wax and 3% of stearic acid into a primary oxidation reactor, gradually heating the preheated Fischer-Tropsch wax and the stearic acid to 120 ℃ to completely melt the Fischer-Tropsch wax and the stearic acid, feeding air into the primary oxidation reactor from an air compressor through a flowmeter, and introducing air with the flow rate of 16.6mL/min g to perform catalytic oxidation. Under the action of the gear pump, the liquid-phase reactant enters a secondary oxidation reactor and continues catalytic oxidation with the introduced air. Wherein the aperture of the inorganic membrane reaction devices in the first-stage oxidation reactor and the second-stage oxidation reactor is 0.5um, the reaction temperature is 170 ℃, and the reaction time is 4 hours, so that the oxidized wax A4-A6 is obtained. The acid number, saponification number, ester number and ester-to-acid ratio performance parameters of the oxidized waxes A4 to A6 are shown in Table 2.
TABLE 2 Performance parameters of oxidized waxes A4 to A6
| Acid value (mgKOH/g) | Soap value (mgKOH/g) | Ratio of ester to acid | |
| Example 4 (starting Material 1) | 35.55 | 90.99 | 1.55 |
| Example 5 (starting material 2) | 52.52 | 120.31 | 1.29 |
| Example 6 (raw material 3) | 61.31 | 141.08 | 1.30 |
Examples 7 to 9
Preheating Fischer-Tropsch wax and 3% of stearic acid in a storage tank, then feeding the preheated Fischer-Tropsch wax and 3% of stearic acid into a primary oxidation reactor, gradually heating the preheated Fischer-Tropsch wax and the stearic acid to 120 ℃ to completely melt the Fischer-Tropsch wax and the stearic acid, feeding air into the primary oxidation reactor from an air compressor through a flowmeter, and introducing air with the flow rate of 13.33mL/min g to perform catalytic oxidation. Under the action of the gear pump, the liquid-phase reactant enters a secondary oxidation reactor and continues catalytic oxidation with the introduced air. Wherein the aperture of the inorganic membrane reaction devices in the first-stage oxidation reactor and the second-stage oxidation reactor is 0.5um, the reaction temperature is 170 ℃, and the reaction time is 4 hours, so that the oxidized wax A7-A9 is obtained. The acid number, saponification number, ester number and ester-to-acid ratio performance parameters of the oxidized waxes A7-A9 are set forth in Table 3.
TABLE 3 Performance parameters of oxidized waxes A7 to A9
| Acid value (mgKOH/g) | Soap value (mgKOH/g) | Ratio of ester to acid | |
| Example 7 (starting material 1) | 21.32 | 64.98 | 2.05 |
| Example 8 (starting material 2) | 43.68 | 113.47 | 1.59 |
| Example 9 (raw material 3) | 54.23 | 120.59 | 1.22 |
Example 10
Substantially the same as in example 1, except that the oxidation reaction temperature was set to 120 ℃ and the reaction time was 4 hours.
Example 11
Substantially the same as in example 1, except that the oxidation reaction temperature was set to 180 ℃ and the reaction time was 4 hours.
Example 12
The flow rate of air was 6.6mL/min g, substantially the same as in example 1.
Example 13
The flow rate of air was 33.3mL/min g, in substantially the same manner as in example 1.
Example 14
The flow rate of air was 20mL/min g in substantially the same manner as in example 1.
TABLE 4 Performance parameters of oxidized waxes A10 to A14
| Acid value (mgKOH/g) | Soap value (mgKOH/g) | Ratio of ester to acid | |
| Example 10 (starting Material 1) | 4.95 | 15.01 | 2.03 |
| Example 11 (starting material 1) | 26.74 | 68.35 | 2.56 |
| Example 12 (starting material 1) | 16.59 | 56 | 3.38 |
| Example 13 (raw material 1) | 25.98 | 60.02 | 2.31 |
| Example 14 (starting material 1) | 28 | 86.40 | 3.09 |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the Fischer-Tropsch wax oxidation method can realize oxidation reaction in a short time, and the quality of the obtained oxidation product is greatly improved. The ester value of the oxidized wax is 50-200 mgKOH/g; the acid value is 20-80 mgKOH/g; the ratio of ester to acid is > 1, preferably 1.2 to 3.2. The tail gas generated in the oxidation process can be safely discharged, the obtained product has light color and no pungent smell, and the requirements of wax products in the application fields of emulsibility, oil solubility, lubricity, pigment dispersibility and the like are completely met.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A continuous non-catalytic oxidation fischer-tropsch wax system, comprising:
the raw material unit comprises a Fischer-Tropsch wax storage tank and an auxiliary agent storage tank, wherein heating equipment for heating a solid-phase raw material into a liquid-phase raw material is arranged outside the Fischer-Tropsch wax storage tank and the auxiliary agent storage tank;
the graded oxidation unit comprises at least two stages of oxidation reactors connected in series, a gas-liquid separator for performing gas-liquid separation on effluent of the oxidation reactor is arranged at the downstream of each stage of oxidation reactor, and the oxidation reactor at the first stage is communicated with the Fischer-Tropsch wax storage tank and the auxiliary agent storage tank through pipelines;
and the tail gas treatment unit is communicated with the gas-phase outlets of the gas-liquid separators at all stages.
2. The continuous, non-catalytic oxidation Fischer-Tropsch wax system of claim 1, wherein the oxidation reactor is a 2-3 stage series oxidation reactor.
3. The continuous non-catalytic oxidation Fischer-Tropsch wax system of claim 1, wherein a filter for filtering impurity metals in the liquid phase feedstock is disposed between the Fischer-Tropsch wax storage tank, the auxiliary storage tank and the oxidation reactor.
4. The continuous catalytic-free oxidation Fischer-Tropsch wax system according to claim 1, wherein the oxidation reactor is provided with a liquid-phase feed inlet and an air inlet at the lower part, and is provided with an outlet material at the top; the discharge hole of the oxidation reactor of the first stage is communicated with the gas-liquid separator of the first stage through a pipeline, the liquid phase outlet of the gas-liquid separator of the first stage is communicated with the liquid phase feed inlet of the oxidation reactor of the next stage through a pipeline, and the liquid phase outlet of the oxidation reactor of the last stage is communicated with the finished product box.
5. The continuous non-catalytic oxidation Fischer-Tropsch wax system of claim 4, wherein the air inlet of the oxidation reactor is provided with an inorganic membrane gas distribution device for uniform dispersion of air within the oxidation reactor;
preferably, the pore diameter of the inorganic membrane in the inorganic membrane gas distribution device is 0.3 to 2.0 μm, preferably 0.3 to 1.0 μm.
6. The continuous non-catalytic oxidation Fischer-Tropsch wax system of claim 1, wherein the tail gas treatment unit comprises a water wash column, an oil-water separator, and a recycle water line in communication.
7. A process for the continuous non-catalytic oxidation of fischer-tropsch wax, comprising the steps of:
respectively preheating and melting Fischer-Tropsch wax and an auxiliary agent, mixing the molten Fischer-Tropsch wax and the auxiliary agent as liquid-phase raw materials, and introducing the liquid-phase raw materials into at least two stages of oxidation reactors connected in series for a non-catalytic oxidation reaction;
after the gas-liquid separation, the effluent of the first stage oxidation reactor enters the next stage oxidation reactor to continue the non-catalytic oxidation reaction until the last stage oxidation reactor finishes the reaction, the liquid phase product is discharged as oxidized wax product, and the gas phase of the effluent of each stage oxidation reactor after the gas-liquid separation is washed with water and discharged.
8. The method of claim 7, wherein the oxidation reactor is a 2-3 stage oxidation reactor in series;
preferably, when the liquid phase raw materials are mixed and introduced into at least two stages of oxidation reactors connected in series, the method further comprises introducing air into the oxidation reactors, wherein the air is dispersed into the liquid phase raw materials through an inorganic membrane gas distribution device;
more preferably, the flow rate of the air is 6.6 to 33.3mL/min g, preferably 13.33 to 20mL/min g; wherein the flow rate represents the flow rate relative to 1g of Fischer-Tropsch wax air;
more preferably, the pore diameter of the inorganic membrane in the inorganic membrane gas distribution device is 0.3 to 2.0. Mu.m, preferably 0.3 to 1.0. Mu.m.
9. The method of claim 7, wherein the Fischer-Tropsch wax is at least one selected from the group consisting of 52#, 60#, 70#, 80#, 90#, 105#, 110#, and 115# Fischer-Tropsch wax; the auxiliary agent is one or more of stearic acid, glacial acetic acid, citric acid and oxidized Fischer-Tropsch wax.
10. The process according to claim 7, characterized in that the temperature of the non-catalytic oxidation reaction is between 120 and 180 ℃, preferably between 150 and 170 ℃; the time of the non-catalytic oxidation is 1 to 4 hours, preferably 1.5 to 3 hours;
preferably, the preheating melting temperature is 100-180 ℃.
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