Device and method for measuring wax oxidation reaction heat
阅读说明：本技术 一种蜡氧化反应热的测定装置及方法 (Device and method for measuring wax oxidation reaction heat ) 是由 钱震 高源� 周岩 杨帆 李俊诚 王海国 解利军 王祯绮 陈祺 于 2021-09-30 设计创作，主要内容包括：本发明提供了一种蜡氧化反应热的测定装置,包括：保温箱；设置在所述保温箱内部的反应器,所述反应器设置有进气管路、出气管路、加热装置、挡板和搅拌装置。本发明提供的测定石蜡或费托蜡氧化反应热的装置,可准确测得蜡氧化过程中的反应热,可为蜡氧化工艺进一步放大提供参考。本发明还提供了一种蜡氧化反应热的测定方法。(The invention provides a device for measuring wax oxidation reaction heat, comprising: a heat preservation box; the reactor is arranged in the heat insulation box and is provided with an air inlet pipeline, an air outlet pipeline, a heating device, a baffle and a stirring device. The device for measuring the oxidation reaction heat of the paraffin or Fischer-Tropsch wax can accurately measure the reaction heat in the wax oxidation process, and can provide reference for further amplification of the wax oxidation process. The invention also provides a method for measuring wax oxidation reaction heat.)
1. An apparatus for measuring wax oxidation reaction heat, comprising:
a heat preservation box;
the reactor is arranged in the heat insulation box and is provided with an air inlet pipeline, an air outlet pipeline, a heating device, a baffle and a stirring device.
2. The apparatus for measuring wax oxidation reaction heat according to claim 1, wherein a heat insulating material is provided outside the reactor.
3. The apparatus for measuring the heat of oxidation reaction of wax according to claim 1, wherein the gas inlet line is provided at the top inlet of the reactor and the gas outlet line is provided at the top outlet of the reactor.
4. The apparatus for measuring wax oxidation reaction heat according to claim 1, wherein the heating means is provided at the bottom of the reactor.
5. The apparatus for measuring wax oxidation reaction heat according to claim 1, wherein the baffle is a double-layer baffle.
6. The apparatus for measuring wax oxidation reaction heat according to claim 1, wherein the baffle is a stainless steel net.
7. The apparatus for measuring wax oxidation reaction heat according to claim 1, wherein the baffle is provided in a middle portion of the reactor.
8. The apparatus for measuring wax oxidation reaction heat according to claim 1, wherein the stirring device is provided inside the reactor.
9. A method for measuring wax oxidation reaction heat, comprising:
the measurement was carried out by using the apparatus for measuring wax oxidation reaction heat according to claim 1.
10. The method of claim 9, comprising:
wax is put into a reactor for oxidation reaction, and according to the air flow F, the air temperature T1 at the inlet of an air inlet pipeline, the air temperature T2 at the outlet of an air outlet pipeline, the specific heat capacity Cp of air, the heat dissipation W0 of a system and the heat W1 taken by air in the reaction process, the heat W2 taken by stirring, the heat W3 of a heating device and the reaction time T, the reaction heat Q is calculated.
Technical Field
The invention belongs to the technical field of wax oxidation reaction, and particularly relates to a device and a method for measuring wax oxidation reaction heat.
Background
In the oxidation process of the raw material wax, polar groups such as-OH, -COOH, -CHO, -COC-, -COOR and the like are introduced on non-polar groups, so that the structure of the internal carbon chain of the oxidized wax and the surface property are changed, and the performances such as dissolution, emulsification, lubrication and the like are greatly improved.
At present, three industrial manufacturers for domestic oxidation mainly produce oxidized wax with an acid value of 7-15 mgKOH/g, such as a United states science and technology limited company; production of oxidized wax with acid values of 16mgKOH/g and 18mgKOH/g by Yimei new material science and technology Limited; shanxi Lu' an refined wax chemical Co., Ltd. produced oxidized wax having an acid value of 30 mgKOH/g.
In the international market, 3 oxidized fischer-tropsch wax products were produced by South African SASOL (SASOL) paraffin wax and surfactant companies; the grades are A28 (acid value 27-29 mgKOH/g), A2 (acid value 9-13 mgKOH/g) and A859 (acid value 3-7 mgKOH/g).
The existing wax oxidation modification includes non-catalyst oxidation and catalyst oxidation, and the quality of the oxidized wax depends on the performance of the catalyst (if any), the control of the reaction temperature, the length of the reaction time and the size of the air flow rate. The reaction heat data is an important basic parameter for controlling the reaction temperature and designing a chemical process, and is accompanied by a relatively obvious heat effect in the oxidation reaction process taking paraffin or Fischer-Tropsch wax as a raw material, which is undoubtedly not negligible in the process amplification process; but the accurate determination of the reaction heat has certain difficulty, and no relevant report is found in China.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a device and a method for measuring wax oxidation reaction heat, which can measure the reaction heat in the wax oxidation process more accurately.
The invention provides a device for measuring wax oxidation reaction heat, comprising:
a heat preservation box;
the reactor is arranged in the heat insulation box and is provided with an air inlet pipeline, an air outlet pipeline, a heating device, a baffle and a stirring device.
Preferably, the reactor is externally provided with a heat insulating material.
Preferably, the gas inlet pipeline is arranged at the top inlet of the reactor, and the gas outlet pipeline is arranged at the top outlet of the reactor.
Preferably, the heating device is arranged at the bottom of the reactor.
Preferably, the baffle is a double-layer baffle.
Preferably, the baffle is a stainless steel mesh.
Preferably, the baffle is disposed in the middle of the reactor.
Preferably, the stirring device is arranged inside the reactor.
The invention provides a method for measuring wax oxidation reaction heat, which comprises the following steps:
the wax oxidation reaction heat measuring device in the technical scheme is adopted for measuring.
Preferably, the method for measuring the wax oxidation reaction heat includes:
wax is put into a reactor for oxidation reaction, and according to the air flow F, the air temperature T1 at the inlet of an air inlet pipeline, the air temperature T2 at the outlet of an air outlet pipeline, the specific heat capacity Cp of air, the heat dissipation W0 of a system and the heat W1 taken by air in the reaction process, the heat W2 taken by stirring, the heat W3 of a heating device and the reaction time T, the reaction heat Q is calculated.
The method and the device for measuring the Fischer-Tropsch wax oxidation reaction heat can accurately measure the reaction heat in the wax oxidation process, and provide reference for industrial scale-up design of the wax oxidation process.
Drawings
Fig. 1 is a schematic structural diagram of a wax oxidation reaction heat measurement device according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a device for measuring wax oxidation reaction heat, comprising:
a heat preservation box;
the reactor is arranged in the heat insulation box and is provided with an air inlet pipeline, an air outlet pipeline, a heating device, a baffle and a stirring device.
In the present invention, the heat-insulating box is preferably a heat-insulating box.
The heat insulation box is not particularly limited, and the heat insulation box known to those skilled in the art can be used for providing a heat insulation environment. The shape and the size of the heat insulation box are not particularly limited, and a person skilled in the art can select the heat insulation box with a proper size and shape according to actual conditions, can be used for containing a reactor and can perform heat insulation on the reactor.
In the present invention, the reactor is used for carrying out an oxidation reaction of wax.
In the present invention, the material of the reactor is preferably stainless steel, and more preferably 304 stainless steel.
In the present invention, the reactor is preferably cylindrical in shape; the diameter of the reactor is preferably 125-135 mm, more preferably 128-132 mm, and most preferably 130 mm; the height is preferably 230 to 250mm, more preferably 235 to 245mm, and most preferably 240 mm.
In the invention, the reactor is provided with an air inlet pipeline which is arranged at an inlet at the top of the reactor and is communicated with the interior of the reactor.
In the invention, the gas inlet pipeline is used for introducing gas such as inert gas (nitrogen, argon and the like) into the reactor to protect the material flow in the system; or gases required for the reaction, such as air, oxygen, etc.
In the invention, the air inlet pipeline is preferably a three-way pipe, a first port of the three-way pipe is used for entering air, a second port of the three-way pipe is used for detecting the temperature of the entering air, a third port of the three-way pipe is used for entering the air into the reactor, and the third port of the three-way pipe is communicated with the inside of the reactor.
In the present invention, the material of the air intake pipe is preferably stainless steel, and more preferably 304 stainless steel. The size of the gas inlet pipeline is not particularly limited, and a person skilled in the art can select the gas inlet pipeline with a proper size according to actual conditions, so that the gas can enter the reactor.
In the invention, an aeration head is also arranged in the reactor, the aeration head is arranged at the bottom of the reactor, an inlet of the aeration head is communicated with an air inlet pipeline, and an outlet of the aeration head is communicated with the inside of the reactor. In the invention, the aeration head is used for gas distribution, and the gas-liquid mass transfer effect of the system can be enhanced.
In the invention, the reactor is provided with an air outlet pipeline, the air outlet pipeline is arranged at an outlet at the top of the reactor, one end of the air outlet pipeline is communicated with the inside of the reactor, and the other end of the air outlet pipeline is provided with an opening.
In the invention, the gas outlet pipeline is used for keeping the pressure of the system stable and discharging the inert gases which are not needed by the reaction and the tail gas generated by the reaction.
In the present invention, the material of the outlet pipe is preferably stainless steel, and more preferably 304 stainless steel. The size of the gas outlet pipeline is not particularly limited, and a person skilled in the art can select the gas outlet pipeline with a proper size according to actual conditions, so that the gas in the reactor can be discharged.
In the invention, a heat preservation device is preferably arranged outside the air outlet pipeline, and an electric tracing band is more preferably arranged outside the air outlet pipeline; the heat preservation device is used for preventing wax carried by the air outlet pipeline from solidifying so as to block the pipeline; the setting temperature of the heat preservation device in the oxidized wax preparation process is preferably 95-105 ℃, and more preferably 100 ℃.
In the present invention, the reactor is provided with a heating device, preferably arranged at the bottom of the reactor, which provides the reactor with the temperature required for the reaction.
In the present invention, the heating means is preferably an electric heating rod; the resistance of the electric heating rod is preferably 65-79 omega, and more preferably 66-68 omega; the power of the electric heating rod is preferably 730-740W, and more preferably 733-735W.
In the invention, the reactor is provided with a stirring device, the stirring device is preferably arranged in the reactor, and the stirring device can enhance the liquid flow in the reactor and enhance the gas-liquid mass transfer effect.
In the present invention, the stirring device is preferably a stirring paddle.
In the present invention, the reactor is provided with a baffle, which is preferably arranged in the middle of the reactor.
In the invention, the baffle plate can prevent the exhaust pipeline from being blocked due to liquid splashing in the reactor.
In the invention, the baffle plates are preferably double-layer baffle plates, the distance between the first layer of baffle plates and the second layer of baffle plates is preferably 40-60 mm, more preferably 45-55 mm, and most preferably 50mm, and the distance can be set according to the height of the reactor.
In the present invention, the baffle is preferably a stainless steel mesh.
In the present invention, the size of the baffle plate is preferably the same as the area of the cross section of the reactor to be able to block splashing of the liquid in the reactor; the baffle is preferably circular in shape and preferably has a diameter that is the same as the inside diameter of the reactor, so that the edge of the stainless steel mesh is in close proximity to the inside wall of the reactor.
In the invention, the thickness of the baffle plate is preferably 2-4 mm, more preferably 2.5-3.5 mm, and most preferably 3 mm. In the invention, the aperture of the baffle (stainless steel net) is preferably 90-110 microns, more preferably 95-105 microns, and most preferably 100 microns.
In the present invention, the outside of the reactor is preferably provided with a heat insulating material.
In the invention, the heat insulating material is preferably selected from one or more of polyurethane foam, polystyrene board, EPS, XPS, phenolic foam, ceramic fiber blanket, aluminum silicate felt, alumina, silicon carbide fiber, aerogel felt, glass wool and rock wool.
In the invention, the thickness of the heat insulation material is preferably 50-70 mm, more preferably 55-65 mm, and most preferably 60 mm.
The invention provides a method for measuring wax oxidation reaction heat, which comprises the following steps:
the wax oxidation reaction heat measuring device in the technical scheme is adopted for measuring.
In the present invention, the method for measuring the wax oxidation reaction heat preferably includes:
wax is put into a reactor for oxidation reaction, and according to the air flow F, the air temperature T1 at the inlet of an air inlet pipeline, the air temperature T2 at the outlet of an air outlet pipeline, the specific heat capacity Cp of air, the heat dissipation W0 of a system and the heat W1 taken by air in the reaction process, the heat W2 taken by stirring, the heat W3 of a heating device and the reaction time T, the reaction heat Q is calculated.
In the present invention, the wax is preferably paraffin wax or fischer-tropsch wax.
The method of the oxidation reaction is not particularly limited in the present invention, and the oxidation reaction may be carried out by a method of wax oxidation reaction well known to those skilled in the art; the temperature of the wax oxidation reaction is preferably 120-199 ℃, more preferably 130-190 ℃, more preferably 140-180 ℃, more preferably 150-170 ℃, and most preferably 160 ℃. The reaction time is not particularly limited in the present invention, and those skilled in the art can select an appropriate reaction time according to actual needs.
In the invention, because the air or oxygen is at normal temperature when entering the reactor, and approaches the reaction temperature when leaving the reactor, a large amount of heat is taken away, and in order to keep the reaction temperature constant, heat is needed to be supplemented into the reaction system; in a reaction system with good heat insulation, the invention adopts a secondary heat insulation mode, namely the reactor is used for heat preservation and heat insulation, the reactor is arranged in a heat preservation and heat insulation box, and an electric heating rod is arranged in the reactor; the air flow is set to be F, the air inlet temperature T1, the air outlet temperature T2, the specific heat capacity Cp of air, the system heat dissipation amount W0, the air carrying heat amount W1, the stirring carrying heat amount W2, the electric heating rod heat amount W3, the reaction operation time length T and the calculation method of the reaction heat amount Q preferably comprise the following steps:
W0+W1＝W2+W3+Q；
Q＝W0+W1-W2-W3；
W1＝F*Cp*(T2-T1)*t。
in the invention, the W0 is obtained by blank experiments, namely, reaction raw materials are added into a reactor, and oxygen-containing gas required by the reaction is not introduced; heating the reaction raw materials to the reaction temperature by adopting a heating device, and calculating by using a heat balance equation of material absorption heat and electric heating heat to obtain W0.
In the present invention, the air flow rate F is preferably detected by a mass flow meter which detects the air flow rate at the inlet of the intake pipe.
In the present invention, the outlet air temperature T2 of the outlet pipeline refers to the outlet air temperature of the outlet pipeline after the reaction is finished.
In the present invention, the method of detecting the reaction time t is preferably a stopwatch record, and the reaction time is a predetermined time.
In the invention, the detection method of the stirring brought-in heat W1 is preferably to test the motor power of the stirring device by a power meter according to the efficiency coefficient of the stirring device; the stirring heat brought by multiplying the motor power and the efficiency coefficient is obtained, the stirring heat brought by the motor power and the efficiency coefficient is generally very small, and the stirring heat brought by the motor power and the efficiency coefficient can be ignored in the actual test process.
In the invention, the method for detecting the heating quantity W3 of the heating device is preferably to test the power of the heating element of the heating device after working by using a power meter according to the efficiency coefficient of the heating device; the heating device heat is obtained by multiplying the heating element power by the efficiency.
The method and the device for measuring the Fischer-Tropsch wax oxidation reaction heat can accurately measure the reaction heat in the wax oxidation process, and provide reference for industrial scale-up design of the wax oxidation process.
Example 1
Fig. 1 is a schematic structural view of the apparatus for measuring wax oxidation reaction heat according to the present embodiment, including:
a heat preservation box;
the reactor is arranged in the heat insulation box, the diameter of the reactor is 128mm, and the height of the reactor is 240 mm;
a three-way pipe is arranged at an inlet at the top of the reactor and is used as an air inlet pipeline, a first port of the three-way pipe is used as an air inlet, a second port of the three-way pipe is used as an inlet for detecting the temperature of inlet air, a third port of the three-way pipe is used as an inlet for gas to flow into the reactor, the third port of the three-way pipe is communicated with an inlet of an aeration head, and an outlet of the aeration head is communicated with the interior of the reactor;
an outlet pipeline is arranged at an outlet at the top of the reactor, one end of the outlet pipeline is communicated with the inside of the reactor, and the other end of the outlet pipeline is provided with an opening; an electric tracing band is arranged outside the air outlet pipeline;
the bottom of the reactor is provided with an electric heating rod;
two layers of stainless steel nets are arranged in the middle of the reactor and used as baffles, the distance between the two layers of stainless steel nets is 50mm, the diameter of the stainless steel nets is the same as that of the reactor, the edges of the stainless steel nets cling to the inner wall of the reactor, and the aperture is 100 microns;
a stirring paddle is arranged in the reactor;
the reactor is externally provided with a heat insulating material (such as polyurethane foam) having a thickness of 60 mm.
Example 2 and example 3 blank test
By using the apparatus for measuring wax oxidation reaction heat provided in example 1, 100# coal-based fischer-tropsch wax was charged into a reactor for oxidation reaction, and the specific method was:
under the condition of stirring by a stirring paddle, heating about 1000g of 100# coal-based Fischer-Tropsch wax to 120 ℃ (heating the Fischer-Tropsch wax to 120 ℃ by a heating rod to completely melt the Fischer-Tropsch wax, and controlling the Fischer-Tropsch wax to be about 150 ℃ (heating the Fischer-Tropsch wax to 150 ℃ by an electric heating rod) without introducing air; measuring the heat dissipation of the system; the system heat removal is shown in table 1.
Table 1 system heat dissipation as measured in examples 2 and 3
Example 2
Example 3
Stirring speed rpm
300
300
Amount of wax g
1200
927
Wax specific heat capacity J/(kg. dot.)
2600
2600
Enthalpy of wax phase transition J/g
160
160
Wax initial temperature C
30.5
19.8
Wax Final temperature C
148.6
150.2
Length of operation min
55
34
Electric quantity kWh of electric heating rod
0.20
0.17
Wax absorption heat J
560472
462610.08
Heat quantity J of electric heating rod
720000
612000
Heat quantity of system
159528
149389.92
And (3) calculating the heat dissipating capacity of the system, wherein the heat balance is as follows:
the heat of the electric heating rod is equal to the heat absorbed by wax plus the heat dissipated by the system;
the system heat dissipation capacity is the heat of the electric heating rod-the wax absorbs the heat;
the heat of the electric heating rod is calculated by the electric quantity of the electric heating rod:
example 1 where the heat of the heating rod was 0.2 x 1000 x 3600 x 720000J,
example 2 electrically heated rod heat 0.17 x 1000 x 3600 x 612000J;
the wax absorbs heat which is sensible heat plus latent heat;
sensible heat wax specific heat wax amount (wax final temperature-wax initial temperature);
latent heat-wax phase transition enthalpy-wax mass.
Example 4 and example 5
By using the apparatus for measuring wax oxidation reaction heat provided in example 1, 100# coal-based fischer-tropsch wax was charged into a reactor for oxidation reaction, and the specific method was:
under the action of a stirring paddle, heating about 1000g of 100# coal-based Fischer-Tropsch wax to 120 ℃ to completely melt the 100# coal-based Fischer-Tropsch wax, introducing air after a system is stable (after the temperature is stable), and carrying out an oxidation reaction, wherein the temperature of the oxidation reaction is gradually increased from 150 ℃ to about 198 ℃; the heat of oxidation reaction was measured, and the results are shown in Table 2.
Table 2 heat of reaction obtained from the tests of example 4 and example 5
Example 4
Example 5
Stirring speed rpm
300
300
Amount of wax g
900
900
Wax specific heat capacity J/(kg. dot.)
2600
2600
Wax temperature increase value DEG C
48
48.5
Air flow rate L/min
1
1
Air inlet temperature deg.C
20
21
Air outlet temperature C
149
150
Air specific heat capacity J/(kg. degreeC.)
1000
1000
Reaction time length min
380
394
Electric quantity kWh of electric heating rod
0.019
0.020
Heat quantity J of electric heating rod
68400
72000
Wax absorption heat J
112320
113490
Air carrying away heat J
63235.8
65565.5
Heat quantity of system
149000
149000
Heat of reaction J
256155.8
256055.5
(Note: the heat dissipation of the system in Table 2 is an approximation of the heat dissipation of the system in example 3 in Table 1)
The acid value of the oxidized wax products of examples 3 and 4 was increased by 9mgKOH/g, the amount of wax was 900g, and the heat of reaction was 11.2W for example 3 and 10.8W for example 4, in terms of conversion.
The method and the device for measuring the oxidation reaction heat of the paraffin wax or Fischer-Tropsch wax can accurately measure the reaction heat in the wax oxidation process, and can provide reference for further amplification of the wax oxidation process. The method can conveniently, quickly and accurately measure the reaction heat of the wax oxidation process.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.