CN109942013B - Process for industrially producing aluminum trichloride - Google Patents
Process for industrially producing aluminum trichloride Download PDFInfo
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- CN109942013B CN109942013B CN201910395285.6A CN201910395285A CN109942013B CN 109942013 B CN109942013 B CN 109942013B CN 201910395285 A CN201910395285 A CN 201910395285A CN 109942013 B CN109942013 B CN 109942013B
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Abstract
A process for industrially preparing aluminium trichloride includes such steps as heating the raw materials including aluminium oxide and petroleum coke in self-induction heating furnace, adding aluminium trichloride in chlorination furnace, heating the raw materials in chlorination furnace, adding aluminium trichloride in chlorination furnace, introducing chlorine from bottom of chlorination furnace, uniformly distributing the chlorine on the sieve plate at bottom of chlorination furnace, fluidizing the aluminium oxide, petroleum coke and aluminium powder, quickly cooling, collecting aluminium trichloride, discharging slags from bottom of chlorination furnace, and absorbing tail gas by three-stage spray.
Description
Technical Field
The invention belongs to the field of inorganic fine powder materials, and particularly relates to a process for industrially producing aluminum trichloride.
Background
Aluminum trichloride is an important inorganic chemical, and industrial products of the aluminum trichloride contain green light yellow particles or powder, have the relative density of 2.44 grams per cubic centimeter (25 ℃), the apparent density of 1.23 grams per cubic centimeter, the melting point of 190 ℃ (0.25MPa), have strong water absorbability, are extremely easy to deliquesce, are easy to absorb water in exposed air to decompose to generate hydrogen chloride, are easy to explode when hydrolyzed by water or water vapor, and have strong corrosivity, and the aluminum trichloride is widely applied to the fields of petrochemical industry and the like.
Most of domestic aluminum trichloride production plants adopt an aluminum ingot melting method, namely, the aluminum ingot is heated and melted, is put into a chlorination reaction furnace to react with introduced chlorine, and is sublimated and condensed to prepare the aluminum trichloride. The reaction heat of 895.5KJ/mol is strong exothermic reaction when the aluminum ingot reacts with chlorine alone, the temperature in the chlorination furnace exceeds more than one thousand ℃, which greatly exceeds the optimized reaction temperature of the reaction of the aluminum ingot and the chlorine, and meanwhile, the temperature resistance of the chlorination furnace equipment is also a big problem. Due to the limitation, in the current industrial production, only a small chlorination furnace can be arranged to control the reaction heat release, the maximum capacity is only 1.2 tons/day through cooling and heat dissipation in the natural environment, the device is not large-scale, and the field operation environment is severe.
In a small part of domestic enterprises, an alumina method is adopted, aluminum oxide powder and petroleum coke are added into a roasting furnace according to a certain proportion for roasting, the roasted material reacts with introduced chlorine, and the product is prepared by purification, cooling and crystallization. Although the reaction of alumina, petroleum coke and chlorine is exothermic, it is not sufficient to maintain the reaction temperature and external heat supply is required. Therefore, a large amount of energy is consumed no matter charging preheating or reaction heating is carried out, the heating temperature generally reaches over 1000 ℃, the requirement on equipment is high, and the investment is large.
No matter which kind of above-mentioned technology, gaseous state aluminium trichloride is all mingled with raw materials, reactant and is got into the trap together, carries out the unloading through regularly knocking trap or crystallizer cooling, and gaseous state aluminium trichloride is caught together with impurity, and product quality does not guarantee. In view of the problems in the prior industrial production of aluminum trichloride, the invention provides a chlorination furnace with lower slag discharge, unreacted raw materials and large-particle impurities are discharged out of a system in time from the lower part of the chlorination furnace, and reaction gas passes through a cyclone dust collector to separate impurities carried by the gas or ultrafine particles of the unreacted raw materials and then enters a quencher so as to ensure that gaseous aluminum trichloride is relatively pure. Furthermore, the invention is provided with three sections of quenching and collecting devices which are connected in series, so that the aluminum trichloride of high-boiling-point substances and low-boiling-point substances carried in the gaseous aluminum trichloride is respectively collected, and the middle section quenching and collecting device obtains a high-purity aluminum trichloride product, thereby avoiding the problem that hydrochloric acid mist is generated due to the contact and moisture absorption of the anhydrous aluminum trichloride product and humid air, greatly improving the packaging environment of the aluminum trichloride product and ensuring that the product does not absorb moisture, and thus, the invention provides a new method for the process for industrially producing the aluminum trichloride.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior system device and process technology for industrially producing the aluminum trichloride, a new method for the process for industrially producing the aluminum trichloride is provided.
The technical scheme of the invention is as follows:
a process for industrially producing aluminum trichloride comprises an electric induction heating furnace, a chlorination furnace containing a chlorine gas sieve plate and a slag discharge pipe, an aluminum powder charging bin, three sections of quenching jackets connected in series, and three aluminum trichloride product bins connected with the quenching jackets, a chlorine introducing pipe, a tail gas pipe, a cyclone separator and a vibrator, wherein reaction raw materials of aluminum oxide and petroleum coke enter the chlorination furnace after being heated by the electric induction heating furnace, the reaction raw materials of aluminum powder enter the chlorination furnace from the aluminum powder charging bin, chlorine gas enters from the bottom of the chlorination furnace through the chlorine introducing pipe, and are uniformly distributed through the sieve plate at the bottom of the chlorination furnace, so that the aluminum oxide, the petroleum coke and the aluminum powder are in a fluidized state in the chlorination furnace, react at high temperature to generate aluminum trichloride, aluminum trichloride products with different specifications are respectively collected in a closed manner through quenching, the chlorination furnace slag is discharged from the bottom of the chlorination furnace, and the tail gas is:
a. preheating: heating a mixture of 150-170 parts by weight of reaction raw material alumina and 75-85 parts by weight of reaction raw material petroleum coke to 800-1000 ℃ through an electric induction heating furnace; the granularity of the alumina serving as the reaction raw material is 60-150 mu m, and the granularity of the petroleum coke is 100-150 mu m;
b. mono-chlorination: introducing chlorine gas, controlling the flow rate of the chlorine gas in a chlorination furnace to be 0.1-0.55 m/s, continuously feeding the hot mixture of the alumina and the petroleum coke heated to 800-1000 ℃ into the chlorination furnace, and carrying out fluidized reduction chlorination on the hot mixture and 320-340 parts by weight of reaction raw material chlorine gas which is uniformly distributed from the bottom of the chlorination furnace through a sieve plate;
c. combined chlorination: when the temperature of a shell of a chlorination furnace reaches 450 ℃, aluminum powder enters the chlorination furnace from different positions through three feeding ports and is put into the chlorination furnace for combined chlorination, meanwhile, the specific gravity of alumina and petroleum coke is correspondingly reduced, and finally, the combined chlorination is carried out at the reaction temperature of 800-850 ℃ under the conditions that the weight of 105-115 parts of alumina, 52-57 parts of petroleum coke, 320-340 parts of chlorine and 25-30 parts of aluminum powder in the chlorination furnace are controlled; the granularity of the aluminum powder serving as the reaction raw material is 3-5 mm;
d. heat balance: after the combined chlorination process is carried out, along with the gradual increase of aluminum powder input by the system, the heating power of the electric induction heating furnace is gradually reduced to maintain the reaction temperature in the chlorination furnace at 800-850 ℃, when the heat release quantity of the aluminum powder and the chlorine and the heat demand quantity for reduction of the aluminum oxide and the chlorine reach balance, the electric induction heating furnace stops heating, the DCS system controls the addition of each reaction raw material to simultaneously ensure the fluidized reaction state in the chlorination furnace and the heat balance and reaction temperature stability of the reaction system, and the whole process system stably operates;
e. three-stage countercurrent quenching and collection: after removing superfine powder impurities carried in gas by a reaction product gaseous aluminum trichloride through a cyclone separator, enabling the gaseous aluminum trichloride to enter three sections of quenching jackets connected in series to exchange heat with countercurrent cooling water, controlling different cooling temperatures of the quenching jackets, and hermetically collecting aluminum trichloride containing high-boiling-point substances, high-purity aluminum trichloride and aluminum trichloride containing low-boiling-point substances through three aluminum trichloride bins respectively, so that the classification of the products of the aluminum trichloride is facilitated, the problem that hydrochloric acid mist is generated due to the fact that anhydrous aluminum trichloride products are contacted with humid air to absorb moisture is avoided, the packaging environment of the aluminum trichloride products is greatly improved, and the aluminum trichloride products are guaranteed not to absorb moisture;
f. slag discharge and tail gas treatment: the slag in the chlorination furnace is discharged from the bottom of the chlorination furnace, the tail gas enters a three-stage spray absorption tower for absorption, aluminum trichloride or other impurities are removed through primary water washing respectively, the generated aluminum trichloride aqueous solution is sent to a polyaluminium chloride workshop, hydrochloric acid mist is absorbed through secondary water spraying, the generated hydrochloric acid is sent to the polyaluminium chloride workshop, and the tertiary alkali absorbs chlorine to generate sodium hypochlorite and then enters a sewage treatment plant for comprehensive treatment.
Furthermore, the electric induction heating furnace is used for heating alumina and petroleum coke during driving, and is only used as a feeding buffer bin after normal operation, if the moisture in the alumina and the petroleum coke is more, the moisture in the alumina and the petroleum coke is removed through electric induction heating, so that the influence on the quality of the aluminum trichloride product is avoided.
Furthermore, the chlorination furnace is a lower-deslagging type chlorination furnace with a sieve plate at the bottom, chlorine gas is introduced firstly, aluminum oxide is added for reaction for a period of time, and then aluminum powder is added for reaction, so that the chlorine gas is uniformly distributed through the sieve plate, and the aluminum oxide, the aluminum powder and the chlorine gas in the chlorination furnace are in a fluidized reaction state.
Furthermore, the chlorination furnace is used for regularly discharging slag at the bottom, so that impurities such as ferric trichloride and heavy metals and unreacted aluminum oxide in the chlorination furnace are discharged and are not brought into a quenching collector by gaseous aluminum trichloride, and the quality of aluminum trichloride products is guaranteed.
Furthermore, the reaction speed of the aluminum powder and the chlorine is high, the reaction speed of the aluminum oxide and the chlorine is low, so the height and diameter of the chlorination furnace are large, the reaction temperature is gradually reduced from bottom to top, the temperatures of the upper section, the middle section and the lower section of the chlorination furnace are controlled through three aluminum powder feeding ports, good reduction chlorination of the aluminum oxide is ensured during heat balance, and the temperatures of the lower section and the upper section of the chlorination furnace are respectively controlled at 840-850 ℃, 830-840 ℃ and 820-830 ℃.
Further, the step of quenching the gaseous aluminum trichloride which is the reaction product into three sections of quenching jackets which are connected in series in a countercurrent manner comprises the following steps: cooling water with the temperature of 10-30 ℃ enters a third quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at the temperature of 200 ℃, then the effluent water with the temperature of 50 ℃ enters a second quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at the temperature of 280 ℃, and the effluent water with the temperature of 70 ℃ enters a first quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at the temperature of 360 ℃; due to the fact that large-temperature-difference three-section countercurrent heat exchange is carried out and different cooling temperatures are controlled, the first aluminum trichloride bin, the second aluminum trichloride bin and the third aluminum trichloride bin are respectively used for hermetically collecting aluminum trichloride containing high-boiling-point substances such as ferric trichloride, high-purity aluminum trichloride and aluminum trichloride containing low-boiling-point substances such as silicon tetrachloride and titanium tetrachloride, so that high-purity aluminum trichloride products can be obtained in the second bin, and the crystal particle sizes of the aluminum trichloride products in the first aluminum trichloride bin, the second aluminum trichloride bin and the third aluminum trichloride bin are respectively 2-5 mm, 3-6 mm and 4-8 mm.
Further, when the whole process system starts to operate, the initial temperature of the electric induction heating furnace for pre-heating the aluminum oxide and the petroleum coke is 900-1000 ℃, which is higher than the normal mono-chlorination reaction temperature by 800-850 ℃, and the partial heat is used for heating the shell of the chlorination furnace; chlorine is introduced into the chlorination furnace, aluminum oxide fed into the electric induction heating furnace is subjected to monochlorination reaction, the reaction lasts for a long time, and due to the fact that a shell of the chlorination furnace absorbs heat, the unreacted chlorine in the system is possibly more, and a subsequent tail gas system must be completely absorbed; and gradually adding aluminum powder for combined chlorination when the temperature of the shell of the chlorination furnace reaches 400-450 ℃, so as to accelerate the temperature rise of the chlorination furnace until the temperature of the shell of the chlorination furnace reaches 800-850 ℃, stopping heating of the electric induction heating furnace, and balancing the heat of the electric induction heating furnace by using a DCS system control device.
Furthermore, the whole process system is completely sealed, the electric induction heating furnace (the aluminum oxide and petroleum coke feeding bin), the aluminum powder feeding bin and the aluminum trichloride bin are all protected by nitrogen gas sealing or nitrogen introduction, on one hand, solid powder adhered to a pipeline is swept by nitrogen gas, on the other hand, oxygen is reduced to enter and generate side reaction with aluminum, and chlorine gas is further prevented from leaking so as to ensure safe, environment-friendly and efficient operation of the system.
Further, the whole process system stops operating in two situations, namely emergency stop and planned stop: when the system is stopped emergently, the safety protection system immediately cuts off all raw material feeding valves and chlorine gas feeding valves, nitrogen enters from the chlorine feeding pipe, the fluidized state in the chlorination furnace is continuously maintained, the heat removal of the chlorination furnace, the quenching device and the tail gas device is ensured, and meanwhile, chlorine in the system is replaced and is absorbed by a subsequent tail gas system, and the chlorination tail gas system is required to be provided with an emergency power supply to ensure the safety of the system; when the car is planned to stop, the adding amount of the alumina and the petroleum coke is gradually reduced until the feeding is completely stopped, so that the alumina and the petroleum coke can completely react with the chlorine as much as possible, and the material amount in the chlorination furnace after the car is stopped is reduced, thereby facilitating the overhaul and treatment; due to the requirement of ensuring the material fluidization state in the chlorination tower, the unreacted chlorine gas in the system is likely to be more, and the subsequent tail gas system must be completely absorbed; the decrement of the aluminum powder is controlled by a DCS system so as to promote the complete reaction of the alumina and the petroleum coke through the heat release of the aluminum powder, and the influence of the residual aluminum powder is small when the next start is carried out; and stopping introducing chlorine gas at the later stage of parking, and changing nitrogen gas heat dissipation and replacement into nitrogen gas.
The invention has the beneficial effects that:
(1) the raw materials are preheated by the electric induction heating furnace, so that pollution caused by fuels such as diesel oil, coal and the like is avoided, the electric induction heating furnace is simple to operate and convenient for workers to operate, the electric induction heating furnace is convenient for automatic temperature control, and can be used as the heating function of aluminum oxide and petroleum coke during driving, and can be used as a feeding buffer bin only after normal operation, and if the water in the aluminum oxide and the petroleum coke is more, the water in the aluminum oxide and the petroleum coke is removed by electric induction heating, so that the influence on the quality of an aluminum trichloride product is avoided;
(2) the exothermic heat of the reaction of the aluminum powder and the chlorine is taken as the endothermic heat of the reaction of the aluminum oxide and the chlorine, so that the problem that the aluminum powder/aluminum ingot device cannot dissipate heat in time due to large amount of exothermic heat to limit the large-scale chlorination furnace device is solved, and the reaction of the aluminum oxide and the chlorine needs heat under the condition of not needing an external heat source, thereby achieving two purposes;
(3) the lower slag-discharging type and the upper wind separator of the chlorination furnace are combined, inferior large-particle raw materials and impurities such as silicon dioxide, titanium dioxide, manganese oxide and the like are discharged from a lower discharge port, and impurities carried in an aluminum trichloride gas outlet in the fluidized chlorination furnace or unreacted raw material ultrafine particles are separated by cyclone and returned to the fluidized chlorination furnace, so that the quality yield and the product purity of gaseous aluminum trichloride at the top of the chlorination furnace are ensured;
(4) by arranging the quenching jacket for heat dissipation, the contact between anhydrous aluminum trichloride and humid air is avoided, the problem that the existing cooling and collecting device naturally dissipates heat and has poor field operation environment and the problems of moisture absorption and hydrochloric acid mist generation of an aluminum trichloride product are greatly reduced;
(5) by setting three-section collection, the quality of the aluminum trichloride product is further subdivided, the middle-section aluminum trichloride can be used as a medical-grade product, and the rest of the aluminum trichloride is applied to different fields according to different impurity types, so that enterprises can subdivide markets conveniently, and the profits are improved;
(6) the whole process system is completely closed, the electric induction heating furnace (concurrently serving as an alumina and petroleum coke charging bin), the aluminum powder charging bin and the aluminum trichloride bin are all protected by nitrogen gas sealing or nitrogen introduction, on one hand, solid powder adhered to a pipeline is swept by nitrogen gas, on the other hand, oxygen entering and aluminum side reaction are reduced, chlorine gas is ensured not to leak, and the safe, environment-friendly and efficient operation of the whole process device and the system is ensured.
Drawings
FIG. 1 is a system, apparatus and process diagram for the industrial production of aluminum trichloride, wherein 1 the electric induction heating furnace (alumina, petroleum coke charging bin), 2 the chlorination furnace, 3 the aluminum powder charging bin, 4-1, 4-2, 4-3 are respectively the first, second, three quench jackets, 5-1, 5-2, 5-3 are respectively the first, second, three aluminum trichloride product bins, 6 chlorine sieve plate, 7 slag discharge pipe, 8 chlorine inlet pipe, 9 tail gas pipe, 10 cyclone separator, 11-1, 11-2, 11-3 are respectively the first, second, three rappers.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
a. Preheating: 160 parts of reaction raw material alumina with the granularity of 60-150 mu m and 80 parts of reaction raw material petroleum coke with the granularity of 100-150 mu m are respectively proportioned by respective belt weighers and added into a premix bin with a weigher and an electric induction heating furnace through a discharge valve, the mixture is quantitatively fed into the electric induction heating furnace through two belt weighers and a premix bin weigher, the feed amount of the electric induction heating furnace is calculated through the two belt weighers and the premix bin weigher, the premix bin and the electric induction heating furnace are sealed with the outside and continuously filled with nitrogen, nitrogen is replaced during driving, and the nitrogen keeps a certain pressure after driving, so that the chlorine back-flowing of the chlorination furnace is prevented. The mixture is heated to 1000 ℃ by an electric induction heating furnace, and considering that the chlorination furnace integrally needs to absorb heat in the initial reaction stage and unreacted chlorine can take away heat, the temperature of the mixture is properly increased, the start-up time is favorably shortened, and stable monochlorination is quickly achieved. The temperature of the electric induction heating furnace is completed by a control system of the electric induction heating furnace, and signals are transmitted to a DCS (distributed control system) of the device.
b. Mono-chlorination: the chlorination furnace completes nitrogen replacement before feeding, so that oxygen and moisture are prevented from entering a system, side reactions are generated, corrosive liquid is generated, products are polluted, and subsequent equipment is corroded; operating a subsequent quenching device to improve the load of a subsequent tail gas system, mainly improving the alkali circulation volume and the alkali concentration and ensuring the absorption of chlorine gas during the driving; introducing 340 weight of chlorine which is uniformly distributed from the bottom of the chlorination furnace through a sieve plate, wherein the flow rate of the chlorine in the chlorination furnace is 0.5m/s, and continuously putting the thermal mixture of the alumina and the petroleum coke into the chlorination furnace for fluidized reduction chlorination; because the chlorination furnace has huge volume, a heating device of the chlorination furnace body is not adopted for investment, so the monochlorination time is longer, and the temperature of the mixture is controlled to be reduced to 950 ℃ by an electric induction heating furnace along with the reaction.
c. Combined chlorination: the method comprises the following steps of (1) adding 3-5 mm of reaction raw material aluminum powder 27 parts by weight into an aluminum powder feeding bin with a weighing device through a belt scale, calculating the feeding amount of the aluminum powder through a belt scale and an aluminum powder feeding bin weighing instrument, sealing the aluminum powder feeding bin with the outside, continuously introducing nitrogen, replacing the nitrogen before feeding the aluminum powder, keeping the nitrogen at a certain pressure after feeding the aluminum powder, purging a pipeline for feeding the aluminum powder into a chlorination furnace, preventing blockage and avoiding chlorine back-flowing, gradually feeding the aluminum powder to start combined chlorination when the temperature of a shell of the chlorination furnace reaches 450 ℃, feeding the aluminum powder from different positions through three feeding ports, gradually increasing the feeding amount, gradually reducing the feeding amount of alumina and petroleum coke, and carrying out combined chlorination by the chlorination furnace; the aluminum powder input of 27 parts by weight is gradually increased, the increment is controlled to be 5kg/min, the corresponding aluminum oxide decrement is 10kg/min, the petroleum coke decrement is 5k/min, and the control is DCS proportion automatic adjustment. And closely paying attention to the fact that the reaction temperature of the chlorination furnace is controlled to be 800-850 ℃ during combined chlorination, avoiding large fluctuation, increasing the temperature of the discharged mixture of the electric induction furnace when the temperature is too low, reducing the temperature of the discharged mixture of the electric induction furnace when the temperature is too high, and reducing the chlorine introduction amount and supplementing nitrogen to maintain a fluidized state when necessary.
d. Heat balance: after the combined chlorination process is carried out, along with the gradual increase of aluminum powder input by the system, the heating power of the electric induction heating furnace is gradually reduced to maintain the reaction temperature in the chlorination furnace at 800-850 ℃, when the heat release of aluminum powder and chlorine and the heat demand of aluminum oxide and chlorine reduction reach balance when the reaction temperature in the chlorination furnace reaches 107 parts by weight, 54 parts by weight of petroleum coke, 27 parts by weight of aluminum powder and 340 parts by weight of chlorine, the electric induction heating furnace stops heating, the addition of each reaction raw material is dynamically controlled by a DCS system to simultaneously ensure the fluidized reaction state in the chlorination furnace and the heat balance and reaction temperature stability of the reaction system, and the whole process system stably operates; the temperature of the upper, middle and lower sections of the chlorination furnace is controlled through three aluminum powder feed ports, good reduction chlorination conditions of alumina during thermal balance are ensured, and the temperature of the upper, middle and lower sections of the chlorination furnace is respectively controlled to be 840-850 ℃, 830-840 ℃ and 820-830 ℃.
e. Three-stage countercurrent quenching and collection: the countercurrent quenching step of the gaseous aluminum trichloride as the reaction product in three stages of quenching jackets connected in series comprises the following steps: cooling water with the temperature of 10-30 ℃ enters a third quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at the temperature of 200 ℃, then the effluent water with the temperature of 50 ℃ enters a second quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at the temperature of 280 ℃, and the effluent water with the temperature of 70 ℃ enters a first quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at the temperature of 360 ℃; due to the fact that large-temperature-difference three-section countercurrent heat exchange is carried out and different cooling temperatures are controlled, the first aluminum trichloride bin, the second aluminum trichloride bin and the third aluminum trichloride bin are respectively used for hermetically collecting aluminum trichloride containing high-boiling-point substances such as ferric trichloride, high-purity aluminum trichloride and aluminum trichloride containing low-boiling-point substances such as silicon tetrachloride and titanium tetrachloride, so that high-purity aluminum trichloride products are obtained in the second bin, and the crystal sizes of the aluminum trichloride products in the first aluminum trichloride bin, the second aluminum trichloride bin and the third aluminum trichloride bin are respectively 2-5 mm, 3-6 mm and 4-8 mm.
f. Slag discharge and tail gas treatment: the slag in the chlorination furnace is discharged from the bottom of the chlorination furnace, the tail gas enters a three-stage spray absorption tower for absorption, aluminum trichloride or other impurities are removed through primary water washing respectively, the generated aluminum trichloride aqueous solution is sent to a polyaluminium chloride workshop, hydrochloric acid mist is absorbed through secondary water spraying, the generated hydrochloric acid is sent to the polyaluminium chloride workshop, and the tertiary alkali absorbs chlorine to generate sodium hypochlorite and then enters a sewage treatment plant for comprehensive treatment.
Comparative example 2
The difference from the embodiment 1 is that aluminum powder is not added, aluminum oxide and petroleum coke are directly used for independent chlorination, an electric induction heating furnace is required to be used for heating all the time, and the electricity consumption of each ton of aluminum trichloride is about 1500 kw; and secondly, the temperature difference between the upper section, the middle section and the lower section in the chlorination furnace is larger, the retention time of reduction chlorination of alumina is longer, the reaction is incomplete, chlorine cannot be completely reacted, and the load of subsequent quenching collection and tail gas treatment is increased.
Comparative example 3
Compared with the embodiment 1, the method has the advantages that alumina and petroleum coke are not added, aluminum powder is used for independent chlorination, the reaction heat ratio is large, the reaction heat release is more, the heat absorption balance of the alumina and the petroleum coke is avoided, the reaction temperature is too high, and the material of a chlorination furnace is difficult to bear; secondly, aluminum powder is singly chloridized, and because the melting point of aluminum is 660 ℃, the aluminum is melted before reaching the reaction temperature of 800 ℃, and fluidized reaction can not be realized in a chlorination furnace.
Comparative example 4
The difference from the example 1 is that the granularity of the aluminum powder is more than 5mm, the total reaction contact area of the aluminum powder and the chlorine is too small, the reaction speed is low, and the fluidized reaction in the chlorination furnace is difficult to realize.
Comparative example 5
The difference from the embodiment 1 is that the granularity of the aluminum powder is less than 3mm, the crushing cost is high, and fine dust is easy to gather and explode in the charging process, thus threatening the safe production.
Comparative example 6
Compared with the embodiment 1, the difference is that the quenching collector adopts air cooling, the cooling effect is extremely poor, and the gas aluminum trichloride is difficult to be effectively cooled to be a crystal product; and secondly, countercurrent heat exchange with different temperature differences is difficult to realize, different cooling temperatures are difficult to control, and unqualified aluminum trichloride products are difficult to be collected in three product bins respectively.
Claims (8)
1. A process for industrially producing aluminum trichloride is characterized in that: the process for industrially producing the aluminum trichloride comprises an electric induction heating furnace, a chlorination furnace containing a chlorine gas sieve plate and a slag discharge pipe, an aluminum powder feeding bin, three sections of quenching jackets connected in series, and three aluminum trichloride product bins, a chlorine introducing pipe, a tail gas pipe, a cyclone separator and a vibrator which are connected, wherein reaction raw materials of aluminum oxide and petroleum coke enter the chlorination furnace after being heated by the electric induction heating furnace, the reaction raw materials of aluminum powder enter the chlorination furnace from the aluminum powder feeding bin, chlorine gas enters from the bottom of the chlorination furnace through the chlorine introducing pipe, and after being uniformly distributed through the sieve plate at the bottom of the chlorination furnace, the aluminum oxide, the petroleum coke and the aluminum powder are in a fluidized state in the chlorination furnace, the method comprises the following steps of reacting at high temperature to generate aluminum trichloride, hermetically collecting aluminum trichloride products of different specifications through quenching respectively, discharging slag in a chlorination furnace from the bottom of the chlorination furnace, and absorbing and comprehensively utilizing tail gas through three-level spraying, wherein the method specifically comprises the following steps:
preheating: heating a mixture of 150-170 parts by weight of reaction raw material alumina and 75-85 parts by weight of reaction raw material petroleum coke to 800-1000 ℃ through an electric induction heating furnace; the granularity of the alumina serving as the reaction raw material is 60-150 mu m, and the granularity of the petroleum coke is 100-150 mu m;
mono-chlorination: introducing chlorine gas, controlling the flow rate of the chlorine gas in a chlorination furnace to be 0.1-0.55 m/s, continuously feeding the hot mixture of the alumina and the petroleum coke heated to 800-1000 ℃ into the chlorination furnace, and carrying out fluidized reduction chlorination on the hot mixture and 320-340 parts by weight of reaction raw material chlorine gas which is uniformly distributed from the bottom of the chlorination furnace through a sieve plate;
combined chlorination: the reaction speed of the aluminum powder and the chlorine is high, the reaction speed of the aluminum oxide and the chlorine is low, so the height and the diameter of the chlorination furnace are large, the reaction temperature is gradually reduced from bottom to top, the temperatures of the upper section, the middle section and the lower section of the chlorination furnace are controlled through three aluminum powder feeding ports, good reduction chlorination of the aluminum oxide is ensured during heat balance, and the temperatures of the lower section and the upper section of the chlorination furnace are respectively controlled at 840-850 ℃, 830-840 ℃ and 820-830 ℃; when the temperature of a shell of the chlorination furnace reaches 450 ℃, putting aluminum powder into the chlorination furnace through three feeding ports for combined chlorination, simultaneously correspondingly reducing the specific gravity of aluminum oxide and petroleum coke, and finally controlling the weight of 105-115 parts of aluminum oxide, 52-57 parts of petroleum coke, 320-340 parts of chlorine and 25-30 parts of aluminum powder in the chlorination furnace to carry out combined chlorination at the reaction temperature of 800-850 ℃; the granularity of the aluminum powder serving as the reaction raw material is 3-5 mm;
heat balance: after the combined chlorination process is carried out, along with the gradual increase of aluminum powder input by the system, the heating power of the electric induction heating furnace is gradually reduced to maintain the reaction temperature in the chlorination furnace at 800-850 ℃, when the heat release quantity of the aluminum powder and the chlorine and the heat demand quantity for reduction of the aluminum oxide and the chlorine reach balance, the electric induction heating furnace stops heating, the DCS system controls the addition of each reaction raw material to simultaneously ensure the fluidized reaction state in the chlorination furnace and the heat balance and reaction temperature stability of the reaction system, and the whole process system stably operates;
three-stage countercurrent quenching and collection: after removing superfine powder impurities carried in gas by a reaction product gaseous aluminum trichloride through a cyclone separator, enabling the gaseous aluminum trichloride to enter three sections of quenching jackets connected in series to exchange heat with countercurrent cooling water, controlling different cooling temperatures, and hermetically collecting aluminum trichloride containing high-boiling-point substances, high-purity aluminum trichloride and low-boiling-point substances through three aluminum trichloride bins respectively, so that the classification of the aluminum trichloride product is facilitated, the problem that hydrochloric acid mist is generated due to the fact that an anhydrous aluminum trichloride product is in contact with humid air to absorb moisture is avoided, the packaging environment of the aluminum trichloride product is greatly improved, and the aluminum trichloride product is ensured not to absorb moisture;
slag discharge and tail gas treatment: the slag in the chlorination furnace is discharged from the bottom of the chlorination furnace, the tail gas enters a three-stage spray absorption tower for absorption, aluminum trichloride or other impurities are removed through primary water washing respectively, the generated aluminum trichloride aqueous solution is sent to a polyaluminium chloride workshop, hydrochloric acid mist is absorbed through secondary water spraying, the generated hydrochloric acid is sent to the polyaluminium chloride workshop, and the tertiary alkali absorbs chlorine to generate sodium hypochlorite and then enters a sewage treatment plant for comprehensive treatment.
2. The process for industrially producing aluminum trichloride according to claim 1, wherein: the electric induction heating furnace is used as the heating function of the alumina and the petroleum coke when the electric induction heating furnace is started, and is only used as a feeding buffer bin after normal operation, if the situation that the moisture in the alumina and the petroleum coke is more occurs, the moisture in the alumina and the petroleum coke is removed through electric induction heating, so that the influence on the quality of the aluminum trichloride product is avoided.
3. The process for industrially producing aluminum trichloride according to claim 1, wherein: the chlorination furnace is a lower-deslagging chlorination furnace with a sieve plate at the bottom, chlorine gas is introduced firstly, aluminum oxide is added for reaction for a period of time, and then aluminum powder is added for reaction, so that the chlorine gas is uniformly distributed through the sieve plate, and the aluminum oxide, the aluminum powder and the chlorine gas in the chlorination furnace are in a fluidized reaction state.
4. The process for industrially producing aluminum trichloride according to claim 1, wherein: the bottom of the chlorination furnace is periodically discharged, so that ferric trichloride, heavy metal impurities and unreacted aluminum oxide in the chlorination furnace are discharged and are not brought into a quenching collector by gaseous aluminum trichloride, and the quality of aluminum trichloride products is guaranteed.
5. The process for industrially producing aluminum trichloride according to claim 1, wherein: the countercurrent quenching step of the gaseous aluminum trichloride as the reaction product in three stages of quenching jackets connected in series comprises the following steps: cooling water at 10-30 ℃ enters a third quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at 200 ℃, then outlet water at 50 ℃ enters a second quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at 280 ℃, and outlet water at 70 ℃ enters a first quenching jacket to perform countercurrent heat exchange with gaseous aluminum trichloride at 360 ℃; due to the fact that large-temperature-difference three-section countercurrent heat exchange is carried out and different cooling temperatures are controlled, the first aluminum trichloride bin, the second aluminum trichloride bin and the third aluminum trichloride bin respectively collect aluminum trichloride containing high-boiling-point substance ferric trichloride, high-purity aluminum trichloride and aluminum trichloride containing low-boiling-point substance silicon tetrachloride and titanium tetrachloride in a sealed mode, so that high-purity aluminum trichloride products are obtained in the second bin, and the crystal sizes of the aluminum trichloride products in the first aluminum trichloride bin, the second aluminum trichloride bin and the third aluminum trichloride bin are respectively 2-5 mm, 3-6 mm and 4-8 mm.
6. The process for industrially producing aluminum trichloride according to claim 1, wherein: when the whole process system starts to operate, the initial temperature of the electric induction heating furnace for pre-heating aluminum oxide and petroleum coke is 900-1000 ℃, which is higher than the normal mono-chlorination reaction temperature by 800-850 ℃, and the partial heat is used for heating the shell of the chlorination furnace; chlorine is introduced into the chlorination furnace, aluminum oxide fed into the electric induction heating furnace is subjected to monochlorination reaction, the reaction lasts for a long time, and due to the fact that a shell of the chlorination furnace absorbs heat, the unreacted chlorine in the system is possibly more, and a subsequent tail gas system must be completely absorbed; and gradually adding aluminum powder for combined chlorination when the temperature of the shell of the chlorination furnace reaches 400-450 ℃, so as to accelerate the temperature rise of the chlorination furnace until the temperature of the shell of the chlorination furnace reaches 800-850 ℃, stopping heating of the electric induction heating furnace, and balancing the heat of the electric induction heating furnace by using a DCS system control device.
7. The process for industrially producing aluminum trichloride according to claim 1, wherein: the whole process system is completely closed, the electric induction heating furnace, the aluminum powder feeding bin and the aluminum trichloride bin are all protected by nitrogen gas sealing or nitrogen introduction, on one hand, solid powder adhered to a pipeline is swept by nitrogen gas, on the other hand, oxygen entering and aluminum side reaction generation is reduced, and chlorine gas is ensured not to leak, so that the safe, environment-friendly and efficient operation of the system is ensured.
8. The process for industrially producing aluminum trichloride according to claim 1, wherein: the whole process system stops operation and is divided into two situations of emergency stop and planned stop: when the system is stopped emergently, the safety protection system immediately cuts off all raw material feeding valves and chlorine gas feeding valves, nitrogen enters from the chlorine feeding pipe, the fluidized state in the chlorination furnace is continuously maintained, the heat removal of the chlorination furnace, the quenching device and the tail gas device is ensured, and meanwhile, chlorine in the system is replaced and is absorbed by a subsequent tail gas system, and the chlorination tail gas system is required to be provided with an emergency power supply to ensure the safety of the system; when the car is planned to stop, the adding amount of the alumina and the petroleum coke is gradually reduced until the feeding is completely stopped, so that the alumina and the petroleum coke can completely react with the chlorine as much as possible, and the material amount in the chlorination furnace after the car is stopped is reduced, thereby facilitating the overhaul and treatment; due to the requirement of ensuring the material fluidization state in the chlorination tower, the unreacted chlorine gas in the system is likely to be more, and the subsequent tail gas system must be completely absorbed; the decrement of the aluminum powder is controlled by a DCS system so as to promote the complete reaction of the alumina and the petroleum coke through the heat release of the aluminum powder, and the influence of the residual aluminum powder is small when the next start is carried out; and stopping introducing chlorine gas at the later stage of parking, and changing nitrogen gas heat dissipation and replacement into nitrogen gas.
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| CN104671268A (en) * | 2013-11-28 | 2015-06-03 | 常州校果信息服务有限公司 | Method for manufacturing aluminum trichloride from aluminum oxide |
| CN109231248A (en) * | 2018-11-27 | 2019-01-18 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of carburizing chlorination production alchlor |
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| CN104671268A (en) * | 2013-11-28 | 2015-06-03 | 常州校果信息服务有限公司 | Method for manufacturing aluminum trichloride from aluminum oxide |
| CN109231248A (en) * | 2018-11-27 | 2019-01-18 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of carburizing chlorination production alchlor |
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