CN113527037A - Method for continuously producing chloroethane by using supergravity reactor - Google Patents
Method for continuously producing chloroethane by using supergravity reactor Download PDFInfo
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- CN113527037A CN113527037A CN202110961933.7A CN202110961933A CN113527037A CN 113527037 A CN113527037 A CN 113527037A CN 202110961933 A CN202110961933 A CN 202110961933A CN 113527037 A CN113527037 A CN 113527037A
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- hydrochloric acid
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- zinc chloride
- ethanol
- heat exchanger
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- 229960003750 ethyl chloride Drugs 0.000 title claims abstract description 78
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 237
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- CRUISIDZTHMGJT-UHFFFAOYSA-L zinc;dichloride;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Zn+2] CRUISIDZTHMGJT-UHFFFAOYSA-L 0.000 claims abstract description 44
- 239000012071 phase Substances 0.000 claims abstract description 42
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 16
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 235000005074 zinc chloride Nutrition 0.000 claims description 19
- 239000011592 zinc chloride Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000010924 continuous production Methods 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 30
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for continuously producing chloroethane by using a supergravity reactor, which comprises the following steps: feeding a high-concentration zinc chloride-hydrochloric acid catalyst solution into a supergravity reactor from a circulating reboiler, discharging a low-concentration zinc chloride-hydrochloric acid catalyst solution from the supergravity reactor to the circulating reboiler for concentration, and feeding concentrated hydrochloric acid into a heat exchanger; simultaneously feeding ethanol and concentrated hydrochloric acid into a hypergravity reactor for chlorination reaction; and the mixed gas containing the chloroethane generated by the chlorination reaction enters a heat exchanger to exchange heat with concentrated hydrochloric acid, the obtained gas-phase chloroethane crude product is discharged to a supergravity rectifying device, and meanwhile, liquid-phase dilute hydrochloric acid condensed and separated in the heat exchanger enters a dilute hydrochloric acid collecting tank for recycling. The method has the advantages of low chloroethane production cost, continuous production process, miniaturized equipment, high yield and high ethanol conversion rate under the working condition of high yield.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for continuously producing chloroethane by using a supergravity reactor.
Background
In industry, ethanol production is basically carried out in a tank reactor, and there are two main methods. One is a batch kettle type process, concentrated hydrochloric acid and ethanol are put into a stirred tank reactor, and the temperature is raised to react under the action of a catalyst to generate ethyl chloride, however, with the reduction of the concentration of the catalyst zinc chloride, the catalyst solution needs to be periodically concentrated, the post-treatment is difficult, the raw material consumption of the process is high, the ethanol conversion rate is low, and the production efficiency is low.
The other production process is to utilize an analytic tower to analyze concentrated hydrochloric acid, and simultaneously introduce the analyzed hydrogen chloride and ethanol into a reaction kettle filled with a catalyst for heat preservation reaction to realize continuous production of chloroethane. Although this method can realize continuous production, generally 1 ton of concentrated hydrochloric acid with a concentration of 31% can only resolve about 110kg of hydrogen chloride gas due to the constant boiling limit of hydrochloric acid. In addition, in order to ensure the conversion rate of ethanol, a reaction kettle with a large volume and a large amount of catalyst solution are generally needed, and the defects of small capacity, large equipment floor area, easiness in damage, difficulty in maintenance, difficulty in catalyst replacement, high extra energy consumption and the like exist, so that the production cost is increased, and great potential safety hazards exist.
Disclosure of Invention
Problems to be solved by the invention
In order to solve the problems of the production method, the invention provides a method for continuously producing chloroethane by using a supergravity reactor.
Means for solving the problems
[1] The method for continuously producing the chloroethane by using the supergravity reactor is characterized by comprising the following steps of:
(1) heating a high-concentration zinc chloride-hydrochloric acid catalyst solution in a circulating reboiler (A), feeding the high-concentration zinc chloride-hydrochloric acid catalyst solution into a supergravity reactor (B) through catalyst feeding holes (a and B), discharging a low-concentration zinc chloride-hydrochloric acid catalyst solution from a catalyst discharging hole (e) from the supergravity reactor (B) to the circulating reboiler (A) for concentration, and feeding concentrated hydrochloric acid into a heat exchanger (D);
(2) simultaneously feeding ethanol into the supergravity reactor (B) from an ethanol feeding hole (c) and concentrated hydrochloric acid from a concentrated hydrochloric acid feeding hole (d) for chlorination reaction, and simultaneously controlling the circulating flow rate of a zinc chloride-hydrochloric acid catalyst solution in the supergravity reactor (B) and the ethanol feeding flow rate;
(3) the mixed gas containing chloroethane generated by chlorination reaction enters a heat exchanger (D) from a mixed gas discharge hole (f) to exchange heat with concentrated hydrochloric acid, the obtained gas-phase chloroethane crude product is discharged to a supergravity rectifying device from the top of the heat exchanger (D), and meanwhile, liquid-phase dilute hydrochloric acid condensed and separated in the heat exchanger (D) enters a dilute hydrochloric acid collecting tank to be recycled;
(4) and washing and rectifying the gas-phase ethyl chloride crude product in a supergravity rectifying device to generate a liquid ethyl chloride finished product.
[2] The method according to the item [1], wherein the high-concentration zinc chloride-hydrochloric acid catalyst solution in the step (1) is a hydrochloric acid solution with the mass fraction of zinc chloride of 65-70%, wherein the hydrochloric acid concentration is 1-5%, and the temperature is raised to 140-150 ℃ in the circulating reboiler (A).
[3] The method according to the item [1] or the item [2], wherein the low-concentration zinc chloride-hydrochloric acid catalyst solution in the step (1) is a hydrochloric acid solution in which the mass fraction of zinc chloride is 60% to 64%, wherein the hydrochloric acid concentration is 6.5% to 14.5%, and the temperature is 120 ℃ to 135 ℃.
[4] The method according to the item [1] or the item [2], wherein the concentrated hydrochloric acid entering the heat exchanger (D) in the step (1) is gas-phase dilute hydrochloric acid, and the concentration thereof is 7.5% to 18%.
[5] The process according to [1] or [2], wherein the volume ratio of the circulation flow rate of the zinc chloride-hydrochloric acid catalyst solution to the ethanol feed flow rate in the supergravity reactor (B) in the step (2) is (20-40): 1.
[6] The process according to [1] or [2], wherein the concentration of the ethanol in the step (2) is 90% or more, and the feed mass ratio of the ethanol to the concentrated hydrochloric acid is (3.2-5.5): 1.
[7] The method according to the item [1] or the item [2], wherein the temperature of the concentrated hydrochloric acid preheated by the heat exchanger (D) in the step (2) is 70 ℃ to 110 ℃, and the concentration of the concentrated hydrochloric acid is 28% to 31%.
[8] The method according to the item [1] or [2], wherein the supergravity rectification device in the step (3) comprises a supergravity rectifier (E), a warm water tank (F) and a condenser (G).
[9] The method according to [7], wherein the packing in the rotor of the hypergravity rectifying machine (E) comprises at least two layers, wherein the first layer is selected from wire mesh packing, and the second layer or more layers are selected from baffle plates or corrugated packing.
[10] The method according to [1] or [2], wherein the water used for washing in the step (4) is neutral water.
ADVANTAGEOUS EFFECTS OF INVENTION
1. The invention directly utilizes the concentrated hydrochloric acid as a raw material, does not need to independently utilize an analytic tower to analyze hydrogen chloride, simultaneously zinc chloride is a catalyst and a boiling breaker of the concentrated hydrochloric acid, utilizes the concentration difference and the temperature difference of the zinc chloride in a circulating reboiler and a hypergravity reactor, improves the effective resolution rate of the concentrated hydrochloric acid, reduces the consumption of the concentrated hydrochloric acid, simultaneously adopts a hypergravity circulating reaction mode, only needs to ensure that the instantaneous concentration of the catalyst contacted with materials is not less than 60 percent, reduces the usage amount of the zinc chloride, and generally the usage amount of the catalyst is about 15 to 20 percent or less of that of a kettle type reactor.
2. The volume of the circulating reboiler is small, the concentrated hydrochloric acid does not need to be analyzed, and the circulating reboiler can be used as a cooling medium for cooling the mixed gas containing the chloroethane, so that the production energy consumption is greatly reduced.
3. The invention utilizes the supergravity technology to strengthen the chlorination reaction, improve the reaction speed and the conversion rate of ethanol, still can ensure higher conversion rate of ethanol under the working condition of high energy production, and the rectifying device is simultaneously used as a washing and rectifying device, so the post-treatment process is simple.
4. The invention has the advantages of simple operation and control, high productivity, small volume of the used device, small occupied area, simple equipment maintenance and continuous production process, reduces the production cost and improves the production safety.
Drawings
FIG. 1 is a process flow diagram of the continuous process for the production of ethyl chloride according to the present invention.
FIG. 2 is another process flow diagram of the continuous ethyl chloride production process of the present invention.
Description of the reference numerals
A: a recycle reboiler; b: a hypergravity reactor; c: a circulation pump; d: a heat exchanger; e: a hypergravity rectifier; f: a warm water tank; g: a condenser; a: a catalyst feed port; b: a catalyst feed port; c: an ethanol feed port; d: a concentrated hydrochloric acid feed port; e: a catalyst discharge port; f: a mixed gas discharge hole; g: and a gas-phase dilute hydrochloric acid discharge port.
Detailed Description
In the following detailed description, numerous specific details are set forth in order to provide a better understanding of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
< terms and definitions >
In the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the use of "optionally" or "optional" means that certain materials, components, performance steps, application conditions, and the like are used or not used.
In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.
Reference throughout this specification to "a preferred embodiment," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< method of the present invention >
The method utilizes a supergravity technology to continuously produce the chloroethane, and particularly adopts a supergravity reactor to continuously produce the chloroethane, and adopts a supergravity rectifying machine to rectify a reaction product (a gas-phase chloroethane crude product) in the post-treatment step of the reaction product.
The method of the present invention is explained below with reference to fig. 1, and it should be clearly understood by those skilled in the art that the implementation of the present invention is not limited to fig. 1. The materials and production units of the present invention are commercially available if not otherwise specified.
< step (1) >
In the step (1), the high-concentration zinc chloride-hydrochloric acid catalyst solution is heated in a circulating reboiler A, then the high-concentration zinc chloride-hydrochloric acid catalyst solution is fed into a supergravity reactor B through a catalyst feed port a and a catalyst feed port B, the low-concentration zinc chloride-hydrochloric acid catalyst solution is discharged from the supergravity reactor B through a catalyst discharge port e to the circulating reboiler A for concentration, and the concentrated hydrochloric acid enters a heat exchanger D.
The high-concentration zinc chloride-hydrochloric acid catalyst solution is a hydrochloric acid solution with the mass fraction of the zinc chloride of 65-70 percent, preferably 68-70 percent, wherein the concentration of the hydrochloric acid is 1-5 percent, and the temperature is raised to 140-150 ℃ in the circulating reboiler (A).
The low-concentration zinc chloride-hydrochloric acid catalyst solution is a hydrochloric acid solution with the mass fraction of zinc chloride of 60-64 percent, preferably 63-64 percent, wherein the concentration of hydrochloric acid is 6.5-14.5 percent, the temperature is 120-135 ℃, and the temperature is preferably 130-135 ℃.
The mass fraction difference of the zinc chloride of the high-concentration zinc chloride-hydrochloric acid catalyst solution and the low-concentration zinc chloride-hydrochloric acid catalyst solution is about 5%, so that the concentrated hydrochloric acid is effectively promoted to be completely resolved in the supergravity reactor to react with the ethanol.
The volume of the hypergravity reactor B can be selected from 1 to 3, the volume of the circulation reboiler A can be selected from 3 to 10, preferably, the volume of the hypergravity reactor B can be selected from 1.5 to 2, and the volume of the circulation reboiler A can be selected from 4 to 6.
It is also preferred in step (1) to feed the high concentration zinc chloride-hydrochloric acid catalyst solution to the hypergravity reactor B using a circulation pump C. In one embodiment, as shown in fig. 1, the high concentration zinc chloride-hydrochloric acid catalyst solution is fed to the supergravity reactor B through the catalyst feed port a and the catalyst feed port B by the circulation pump C after being warmed to 140 ℃ to 150 ℃ in the circulation reboiler a.
The zinc chloride has water absorption and is a 'boiling breaking agent' of the hydrochloric acid, under the zinc chloride environment, the hydrochloric acid and the water do not form an azeotrope, so that the hydrogen chloride in the concentrated hydrochloric acid (namely the concentrated hydrochloric acid preheated in the step (2)) can be completely desorbed and reacted with the ethanol. The high concentration zinc chloride-hydrochloric acid catalyst solution absorbs the water in the concentrated hydrochloric acid, and then the concentration is reduced to become the low concentration zinc chloride-hydrochloric acid catalyst solution.
As described above, the low concentration zinc chloride-hydrochloric acid catalyst solution is concentrated in the circulation reboiler a to become gas phase diluted hydrochloric acid with a concentration of 7.5% to 18%, and the gas phase diluted hydrochloric acid enters the heat exchanger D.
< step (2) >
In the step (2), ethanol is simultaneously fed into the supergravity reactor B from an ethanol feeding hole c and concentrated hydrochloric acid from a concentrated hydrochloric acid feeding hole d for chlorination reaction, and the circulating flow rate of the zinc chloride-hydrochloric acid catalyst solution in the supergravity reactor B and the ethanol feeding flow rate are controlled at the same time. The feeding mass ratio of the ethanol to the concentrated hydrochloric acid is (3.2-5.5): 1.
in the present invention, as shown in fig. 1, cold concentrated hydrochloric acid (with a concentration of 28% to 31%, normal temperature) is fed into a heat exchanger D, and then fed into a supergravity reactor B from a concentrated hydrochloric acid feed port D to perform chlorination reaction with ethanol.
In the continuous process of the present invention, ethanol and concentrated hydrochloric acid are subjected to chlorination reaction to produce a mixed gas containing chloroethane (shown as "chloroethane mixed gas" in fig. 1), and the mixed gas is fed into a heat exchanger D, while the gas phase diluted hydrochloric acid in step (1) is fed into the heat exchanger D. Therefore, the cold concentrated hydrochloric acid fed into the heat exchanger D is subjected to heat exchange with the mixed gas and the gas-phase dilute hydrochloric acid in the heat exchanger D to form preheated concentrated hydrochloric acid, the temperature after preheating is 70-110 ℃, and the concentration is 28-31%.
The volume ratio of the circulating flow rate of the zinc chloride-hydrochloric acid catalyst solution in the supergravity reactor B to the ethanol feeding flow rate in the step (2) is (20-40):1, and preferably (20-30): 1. The concentration of ethanol in step (2) is 90% or more, preferably 95% liquid industrial ethanol, and is not particularly limited. The feed mass ratio of the ethanol to the concentrated hydrochloric acid is (3.2-5.5):1, preferably (3.5-4.8): 1.
< step (3) >
And (3) introducing the mixed gas containing the chloroethane generated in the chlorination reaction in the step (2) into a heat exchanger D from a mixed gas discharge port f to exchange heat with the cold concentrated hydrochloric acid, discharging the obtained gas-phase chloroethane crude product to a supergravity rectifying device from the top of the heat exchanger D, and simultaneously introducing liquid-phase dilute hydrochloric acid condensed and separated from the gas-phase dilute hydrochloric acid in the heat exchanger D into a dilute hydrochloric acid collecting tank for recycling.
Wherein, the mixed gas containing chloroethane at about 130 ℃ is cooled to about 40 ℃ through heat exchange in a heat exchanger D, most of the by-product water, hydrogen chloride and unconverted ethanol are condensed into dilute hydrochloric acid solution containing ethanol, and the dilute hydrochloric acid solution enters a dilute hydrochloric acid collecting tank. Gaseous chloroethane, a small part of non-condensed by-product water, hydrogen chloride, unconverted ethanol and by-product ether enter a supergravity rectifying device.
The cold concentrated hydrochloric acid, the gas-phase dilute hydrochloric acid and the mixed gas containing chloroethane exchange heat in a heat exchanger D to realize respective condensation separation of the gas-phase dilute hydrochloric acid and the mixed gas, the obtained dilute hydrochloric acid solution is collected by a dilute hydrochloric acid collecting tank for recycling, and meanwhile, the obtained gas-phase chloroethane crude product is washed and rectified in a supergravity rectifying device, so that the product utilization maximization is realized.
< step (4) >
And (4) washing and rectifying the gas-phase ethyl chloride crude product obtained in the step (3) in a supergravity rectifying device to generate a liquid ethyl chloride finished product. The hypergravity rectifying device comprises a hypergravity rectifying machine E, a warm water tank F and a condenser G.
Specifically, as shown in fig. 1, the gas phase ethyl chloride crude product enters a hypergravity rectifying machine E, and simultaneously the washing water, which is neutral water, preferably tap water or neutral soft water, enters the hypergravity rectifying machine E to wash the crude product to remove impurities. The neutral water is used for generating acid washing water after washing and then enters a warm water tank, and the temperature of the warm water tank is controlled to be 20-30 ℃, preferably 25-30 ℃. The ethyl chloride cooled after being washed is re-evaporated into gaseous state by the warm water tank, and the gaseous state passes through the gas phase balance pipe and enters the hypergravity rectifying machine E again for rectification.
Meanwhile, the gas-phase ethyl chloride crude product is rectified in a hypergravity rectifying machine E to generate a gas-phase ethyl chloride finished product (shown as a 'gas-phase finished product' in figure 1), the gas-phase ethyl chloride finished product enters a condenser for condensation, the finished product obtained after condensation enters a finished product tank for later use, and reflux liquid generated by condensation enters the hypergravity rectifying machine E for rectification again.
The continuous production process of ethyl chloride according to the present invention is explained above with reference to fig. 1. It should be noted that, in the production practice, the steps (1) to (4) of the method of the present invention are continuously performed at the same time to complete the continuous process of catalyst feeding, reaction material feeding, material heat exchange in the heat exchanger, and distillation in the distillation device to obtain the finished product. Therefore, the numbers of steps (1) to (4) in the present invention are not used to indicate the sequence between them, but to indicate the respective steps.
FIG. 2 is another process flow diagram of the process of the present invention. As shown in fig. 2, the high concentration zinc chloride-hydrochloric acid catalyst solution is heated in the circulating reboiler, and then fed into the supergravity reactor, the low concentration zinc chloride-hydrochloric acid catalyst solution is discharged from the supergravity reactor to the circulating reboiler for concentration, and the concentrated hydrochloric acid, i.e. gas phase dilute hydrochloric acid, enters the heat exchanger; simultaneously, simultaneously feeding ethanol and concentrated hydrochloric acid into a hypergravity reactor for chlorination reaction; and the mixed gas containing chloroethane generated by the chlorination reaction enters a heat exchanger to exchange heat with cold concentrated hydrochloric acid, and the obtained gas-phase chloroethane crude product is discharged to a supergravity rectifying device to be washed and rectified to generate a liquid chloroethane finished product.
The present invention is further illustrated by the following specific examples. The apparatus used in the present invention is a conventional apparatus unless otherwise specified.
In the examples, the ethanol conversion was calculated as follows: ethyl chloride (in hundred) actual yield ÷ theoretical yield.
For example, 1000g of 95% ethanol has a mass of 950g, a theoretical amount of ethyl chloride converted into ethyl chloride of 1332.07g, and ethyl chloride 1318g having a purity of 99.95%, a water content of 100ppm, and an acidity of 10ppm was actually obtained. Therefore, when the amount of ethyl chloride obtained after removing water, acid and other impurities (i.e., percent conversion) was 1317.18g, the conversion of ethyl chloride was 98.99%.
The effective resolution of concentrated hydrochloric acid was calculated as follows: the theoretical consumption of hydrogen chloride divided by the feeding amount of concentrated hydrochloric acid.
For example, 1000g of 95% ethanol, a theoretical hydrogen chloride consumption of 753.80g for conversion to ethyl chloride and 5000g of 31% concentrated hydrochloric acid feed, gives an effective hydrogen chloride resolution of 15.08%.
Example 1
Simultaneously, the hypergravity reactor and the hypergravity rectifying machine are started, and the rotating speed of the hypergravity reactor and the hypergravity rectifying machine is controlled to be 500-600 r/min. Heating a zinc chloride-hydrochloric acid catalyst solution with the zinc chloride mass fraction of 68% and the hydrochloric acid concentration of 2.5% in a 5-square circulating reboiler to 145 ℃, starting a circulating pump, and controlling the circulating flow to be 7m3H is used as the reference value. The zinc chloride-hydrochloric acid catalyst solution is fed from the circulating reboiler to the supergravity reactor through the circulating pump from the catalyst feed inlet. The catalyst solution becomes a zinc chloride-hydrochloric acid catalyst solution with the mass fraction of zinc chloride of about 63.5% and the hydrochloric acid concentration of about 7.7% after absorbing water in the supergravity reactor, the solution is discharged from the supergravity reactor through a catalyst discharge port to a circulating reboiler for concentration, and the concentrated hydrochloric acid becomes gas-phase dilute hydrochloric acid and enters a heat exchanger.
Meanwhile, ethanol with the concentration of 95% is fed into the hypergravity reactor from an ethanol feeding hole at a feeding speed of 200kg/h and concentrated hydrochloric acid with the concentration of 31% at a feeding speed of 912kg/h through a heat exchanger to carry out chlorination reaction. The volume ratio of the circulating flow rate of the zinc chloride-hydrochloric acid catalyst solution in the hypergravity reactor to the ethanol feeding flow rate is controlled to be 28: 1.
The mixed gas containing chloroethane generated by the chlorination reaction enters a heat exchanger from a mixed gas discharge hole, and exchanges heat with cold concentrated hydrochloric acid (the concentration is 31%) fed into the heat exchanger together with gas-phase dilute hydrochloric acid. Concentrated hydrochloric acid preheated by a heat exchanger (the temperature is 85-105 ℃) is fed into the high-gravity reactor from a concentrated hydrochloric acid feeding hole to carry out chlorination reaction.
The temperature of the gas phase in the heat exchanger reaches 130 DEG CThe catalyst circulation flow is gradually increased to 35m from left to right3The feed rate was increased to 1000kg/h ethanol and 4560kg/h concentrated hydrochloric acid.
The obtained gas-phase ethyl chloride crude product is washed by tap water, the temperature of a warm water tank is controlled to be 30 ℃, and the acid content in the washed washing water is controlled to be less than 5 percent by controlling the flow of the tap water. Condensing the washed gas-phase chloroethane finished product through a condenser to obtain a liquid chloroethane finished product.
In the whole process, after the discharge is stable, the ethanol consumption, the concentrated hydrochloric acid consumption, the chloroethane yield and the chloroethane quality within one hour are calculated, and the results are as follows: the ethanol consumption was 1000kg, the concentrated hydrochloric acid consumption was 4560kg, the ethyl chloride yield was 1309kg, the ethyl chloride purity was 99.91%, the acid value was 14ppm, and the water content was 110 ppm. The conversion rate of the ethanol is calculated to be 98.17 percent, and the effective resolution rate of the concentrated hydrochloric acid is calculated to be 16.53 percent.
Example 2
Simultaneously, the hypergravity reactor and the hypergravity rectifying machine are started, and the rotating speed of the hypergravity reactor and the hypergravity rectifying machine is controlled to be 500-600 r/min. Heating a zinc chloride-hydrochloric acid catalyst solution with the zinc chloride mass fraction of 65% and the hydrochloric acid concentration of 3% in a 5-square circulating reboiler to 140 ℃, starting a circulating pump, and controlling the circulating flow to be 6m3H is used as the reference value. The zinc chloride-hydrochloric acid catalyst solution is fed from the circulating reboiler to the supergravity reactor through the circulating pump from the catalyst feed inlet. The catalyst solution is absorbed by water in the supergravity reactor to become a zinc chloride-hydrochloric acid catalyst solution with the mass fraction of zinc chloride of about 60% and the hydrochloric acid concentration of about 8.8%, the solution is discharged from the supergravity reactor through a catalyst discharge port to a circulating reboiler for concentration, and the concentrated hydrochloric acid becomes gas-phase dilute hydrochloric acid and enters a heat exchanger.
Meanwhile, ethanol with the concentration of 95% is fed into the hypergravity reactor from an ethanol feeding hole at a feeding speed of 200kg/h and concentrated hydrochloric acid with the concentration of 31% at a feeding speed of 1010kg/h through a heat exchanger from a concentrated hydrochloric acid feeding hole at the same time to carry out chlorination reaction. The volume ratio of the circulating flow rate of the zinc chloride-hydrochloric acid catalyst solution in the hypergravity reactor to the ethanol feeding flow rate is controlled to be 24: 1.
The mixed gas containing chloroethane generated by the chlorination reaction enters a heat exchanger from a mixed gas discharge hole, and exchanges heat with cold concentrated hydrochloric acid (the concentration is 31%) fed into the heat exchanger together with gas-phase dilute hydrochloric acid. Concentrated hydrochloric acid preheated by a heat exchanger (the temperature is 70-100 ℃) is fed into the hypergravity reactor from a concentrated hydrochloric acid feed inlet to carry out chlorination reaction.
Gradually increasing the catalyst circulation flow to 45m when the gas phase temperature in the heat exchanger reaches about 132 DEG C3The feed rate was increased to 1500kg/h ethanol and 7575kg/h concentrated hydrochloric acid.
The obtained gas-phase ethyl chloride crude product is washed by tap water, the temperature of a warm water tank is controlled to be 25 ℃, and the acid content in the washed washing water is controlled to be less than 5 percent by controlling the flow of the tap water. Condensing the washed gas-phase chloroethane finished product through a condenser to obtain a liquid chloroethane finished product.
In the whole process, after the discharge is stable, the ethanol consumption, the concentrated hydrochloric acid consumption, the chloroethane yield and the chloroethane quality within one hour are calculated, and the results are as follows: the ethanol consumption was 1500kg, the concentrated hydrochloric acid consumption was 7575kg, the ethyl chloride yield was 1978kg, the ethyl chloride purity was 99.93%, the acid value was 12ppm, and the water content was 97 ppm. The conversion rate of ethanol is calculated to be 98.91 percent, and the effective resolution rate of concentrated hydrochloric acid is calculated to be 14.93 percent.
Example 3
Simultaneously, the hypergravity reactor and the hypergravity rectifying machine are started, and the rotating speed of the hypergravity reactor and the hypergravity rectifying machine is controlled to be 500-600 r/min. Heating a zinc chloride-hydrochloric acid catalyst solution with the zinc chloride mass fraction of 70% and the hydrochloric acid concentration of 1% in a 5-square circulating reboiler to 150 ℃, starting a circulating pump, and controlling the circulating flow to be 5m3H is used as the reference value. The zinc chloride-hydrochloric acid catalyst solution is fed from the circulating reboiler to the supergravity reactor through the circulating pump from the catalyst feed inlet. The catalyst solution absorbs water in the supergravity reactor to become a zinc chloride-hydrochloric acid catalyst solution with the mass fraction of zinc chloride of about 64% and the hydrochloric acid concentration of about 7.5%, the solution is discharged from the supergravity reactor through a catalyst discharge port to a circulating reboiler for concentration, and the concentrated hydrochloric acid becomes gas-phase dilute hydrochloric acid and enters a heat exchanger.
Meanwhile, ethanol with the concentration of 95% is fed into the hypergravity reactor from an ethanol feeding hole at a feeding speed of 200kg/h and concentrated hydrochloric acid with the concentration of 31% is fed into the hypergravity reactor from a concentrated hydrochloric acid feeding hole at a feeding speed of 793.4kg/h through a heat exchanger to carry out chlorination reaction. The volume ratio of the circulating flow rate of the zinc chloride-hydrochloric acid catalyst solution in the hypergravity reactor to the ethanol feeding flow rate is controlled to be 20: 1.
The mixed gas containing chloroethane generated by the chlorination reaction enters a heat exchanger from a mixed gas discharge hole, and exchanges heat with cold concentrated hydrochloric acid (the concentration is 31%) fed into the heat exchanger together with gas-phase dilute hydrochloric acid. Concentrated hydrochloric acid (90-110 ℃) preheated by the heat exchanger is fed into the high-gravity reactor from a concentrated hydrochloric acid feed inlet to carry out chlorination reaction.
Gradually increasing the catalyst circulation flow to 50m when the gas phase temperature in the heat exchanger reaches about 132 DEG C3The feed rate was increased to 2000kg/h ethanol and 7934kg/h concentrated hydrochloric acid.
The obtained gas-phase ethyl chloride crude product is washed by tap water, the temperature of a warm water tank is controlled to be 30 ℃, and the acid content in the washed washing water is controlled to be less than 5 percent by controlling the flow of the tap water. Condensing the washed gas-phase chloroethane finished product through a condenser to obtain a liquid chloroethane finished product.
In the whole process, after the discharge is stable, the ethanol consumption, the concentrated hydrochloric acid consumption, the chloroethane yield and the chloroethane quality within one hour are calculated, and the results are as follows: the ethanol consumption was 2000kg, the concentrated hydrochloric acid consumption was 7934kg, the ethyl chloride yield was 2638kg, the ethyl chloride purity was 99.95%, the acid value was 8ppm, and the water content was 105 ppm. The conversion rate of ethanol is calculated to be 98.96%, and the effective resolution rate of concentrated hydrochloric acid is calculated to be 19.00%.
Industrial applicability
The method for continuously producing the chloroethane by using the supergravity reactor can be used for continuously producing the chloroethane in the actual industry.
Claims (10)
1. A method for continuously producing chloroethane by using a supergravity reactor is characterized by comprising the following steps:
(1) heating a high-concentration zinc chloride-hydrochloric acid catalyst solution in a circulating reboiler (A), feeding the high-concentration zinc chloride-hydrochloric acid catalyst solution into a supergravity reactor (B) through catalyst feeding holes (a and B), discharging a low-concentration zinc chloride-hydrochloric acid catalyst solution from a catalyst discharging hole (e) from the supergravity reactor (B) to the circulating reboiler (A) for concentration, and feeding concentrated hydrochloric acid into a heat exchanger (D);
(2) simultaneously feeding ethanol into the supergravity reactor (B) from an ethanol feeding hole (c) and concentrated hydrochloric acid from a concentrated hydrochloric acid feeding hole (d) for chlorination reaction, and simultaneously controlling the circulating flow rate of a zinc chloride-hydrochloric acid catalyst solution in the supergravity reactor (B) and the ethanol feeding flow rate;
(3) the mixed gas containing chloroethane generated by chlorination reaction enters a heat exchanger (D) from a mixed gas discharge hole (f) to exchange heat with concentrated hydrochloric acid, the obtained gas-phase chloroethane crude product is discharged to a supergravity rectifying device from the top of the heat exchanger (D), and meanwhile, liquid-phase dilute hydrochloric acid condensed and separated in the heat exchanger (D) enters a dilute hydrochloric acid collecting tank to be recycled;
(4) and washing and rectifying the gas-phase ethyl chloride crude product in a supergravity rectifying device to generate a liquid ethyl chloride finished product.
2. The method according to claim 1, wherein the high-concentration zinc chloride-hydrochloric acid catalyst solution in the step (1) is a hydrochloric acid solution with a zinc chloride mass fraction of 65-70%, wherein the hydrochloric acid concentration is 1-5%, and the temperature is raised to 140-150 ℃ in the circulating reboiler (A).
3. The method according to claim 1 or 2, wherein the low concentration zinc chloride-hydrochloric acid catalyst solution in the step (1) is a hydrochloric acid solution with a zinc chloride mass fraction of 60% -64%, wherein the hydrochloric acid concentration is 6.5% -14.5%, and the temperature is 120 ℃ -135 ℃.
4. The process according to claim 1 or 2, characterized in that the concentrated hydrochloric acid entering the heat exchanger (D) in step (1) is a gas-phase dilute hydrochloric acid with a concentration of 7.5% to 18%.
5. The process according to claim 1 or 2, wherein the volume ratio of the circulating flow rate of the zinc chloride-hydrochloric acid catalyst solution to the ethanol feed flow rate in the hypergravity reactor (B) in step (2) is (20-40): 1.
6. The method according to claim 1 or 2, wherein the concentration of the ethanol in the step (2) is 90% or more, and the feed mass ratio of the ethanol to the concentrated hydrochloric acid is (3.2-5.5): 1.
7. The process according to claim 1 or 2, wherein the temperature of the concentrated hydrochloric acid preheated by the heat exchanger (D) in the step (2) is 70-110 ℃, and the concentration is 28-31%.
8. The method according to claim 1 or 2, wherein the supergravity rectification device in step (3) comprises a supergravity rectifier (E), a warm water tank (F) and a condenser (G).
9. The process according to claim 7, characterized in that the packing in the rotor of the hypergravity rectifier (E) comprises at least two layers, wherein the first layer is selected from wire mesh packing and the second or more layers are selected from baffles or corrugated packing.
10. The method according to claim 1 or 2, wherein the water used for washing in step (4) is neutral water.
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| CN114229932A (en) * | 2021-11-23 | 2022-03-25 | 安徽金禾实业股份有限公司 | Device and method for treating acidic wastewater in chloroethane production |
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