CN115261070B - Method for preparing chlorinated paraffin and polyaluminum chloride flocculant in synergistic manner - Google Patents
Method for preparing chlorinated paraffin and polyaluminum chloride flocculant in synergistic manner Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/38—Chemical modification of petroleum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
- C01F7/57—Basic aluminium chlorides, e.g. polyaluminium chlorides
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Abstract
The invention provides a method for preparing chlorinated paraffin and polyaluminum chloride flocculant in a synergistic way, and belongs to the technical field of chlorinated paraffin production. The method specifically comprises the following steps: the chlorine and paraffin oil are treated by low-temperature plasma for the first time to obtain a chlorowax primary product and first tail gas; the chloroparaffin primary product is subjected to degassing treatment to obtain chlorinated paraffin and second tail gas; the first tail gas and/or the second tail gas and the aluminum source slurry are subjected to a second low-temperature plasma treatment to obtain polyaluminum chloride mixed slurry; and centrifuging and drying the polyaluminium chloride mixed slurry to obtain the polyaluminium chloride flocculant. The chlorine and paraffin oil reaction is carried out at normal temperature, additional heating is not needed, a stabilizer is not needed to be added in the degassing process of the prepared chloroparaffin primary product, the limitation on the temperature and quality index of the chlorine and paraffin oil in the preparation process of the chloroparaffin is eliminated, and the chloroparaffin tail gas is efficiently recycled.
Description
Technical Field
The invention belongs to the technical field of chlorinated paraffin production, and particularly relates to a method for preparing chlorinated paraffin and polyaluminum chloride flocculant in a synergistic manner.
Background
Chlorinated paraffin (also called chlorocarbon) is a chlorinated derivative of paraffin, and a chlorinated paraffin raw material is derived from petroleum and is a common large-tonnage fine chemical product. The core of the chlorinated paraffin is C 14 ～C 17 Has no toxicity, has certain chemical inertness and can react with specific esters to form plasticizer. Chlorinated paraffin is not flammable, plays roles of flame retardance, lubrication, corrosion resistance and the like in different application places, and is commonly used as a flame retardant, a binder, a coating, a lubricating oil additive and the like for plastic rubber and textiles.
Chlorinated paraffin products are mainly produced by a thermal chlorination method in the current industry, and paraffin chlorination reaction belongs to free radical substitution chain reaction. The thermal chlorination process is mature, but the preparation process is highly dependent on a heat source for supplying heat, the chlorine and paraffin oil are heated to a certain temperature range in the reaction process, and the generated tail gas is various in types, usually acid-oil blending, and is difficult to treat or recycle, so that the tail gas is treated as waste, and resource waste is caused. Meanwhile, the thermal chlorination process has more severe requirements on raw material quality, and has strict limits on indexes such as chlorine content, chlorine water content, chlorine temperature, impurity content in chlorine, paraffin oil temperature and the like. In addition, chlorinated paraffin semi-finished products have poor stability, and a certain amount of stabilizer needs to be added before degassing.
Therefore, based on the technical problems, the invention provides a method for preparing chlorinated paraffin and polyaluminum chloride flocculant in a synergic manner.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a method for preparing chlorinated paraffin and polyaluminum chloride flocculant in a synergistic way.
In one aspect of the invention, a method for preparing a chlorinated paraffin and polyaluminum chloride flocculant in a synergistic manner is provided, which specifically comprises the following steps:
the chlorine and paraffin oil are treated by low-temperature plasma for the first time to obtain a chlorowax primary product and first tail gas;
the chloroparaffin primary product is subjected to degassing treatment to obtain chlorinated paraffin and second tail gas;
the first tail gas and/or the second tail gas and the aluminum source slurry are subjected to a second low-temperature plasma treatment to obtain polyaluminum chloride mixed slurry;
and centrifuging and drying the polyaluminium chloride mixed slurry to obtain the polyaluminium chloride flocculant.
Optionally, the volume ratio of the chlorine to the paraffin oil is 450-550:1.
Optionally, the action voltage range of the first low-temperature plasma treatment is 25 kV-125 kV.
Optionally, the action voltage range of the second low-temperature plasma treatment is 5 kV-75 kV.
Optionally, the aluminum source slurry is formed by a method comprising:
mixing the aluminum source material with sodium hydroxide solution, and stirring for 0.5-1.5 h to obtain aluminum source slurry.
Optionally, the aluminum source material includes any one or more of calcium aluminate, aluminum hydroxide, bauxite.
Optionally, the first tail gas and the second tail gas each comprise at least one of organic matters, water vapor, chlorine and hydrogen chloride.
Optionally, the chlorinated paraffin is chlorinated paraffin-52.
Optionally, the chlorine content in the chlorinated paraffin ranges from 51% to 53%, and the viscosity of the chlorinated paraffin ranges from 150mPa.s to 250mPa.s.
Optionally, the basicity range of the polyaluminum chloride flocculant is 30% -95%, and the mass fraction of alumina in the polyaluminum chloride flocculant is more than 28%.
According to the invention, the low-temperature plasma irradiation technology is used for converting chloride ions into chlorine free radicals, so that the reaction of chlorine and paraffin oil is carried out at normal temperature, no additional heating is needed, a stabilizer is not needed to be added in the degassing process of the prepared chloroparaffin primary product, the limitation of the temperature and quality index of the chlorine and paraffin oil in the preparation process of the chloroparaffin is eliminated, and the chloroparaffin tail gas is efficiently recycled.
Drawings
FIG. 1 is a flow diagram of a method for the synergistic preparation of chlorinated paraffin and polyaluminum chloride flocculant in accordance with one embodiment of the present invention;
FIG. 2 is a schematic diagram of a process for the synergistic preparation of chlorinated paraffin and polyaluminum chloride flocculant in accordance with another embodiment of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of better understanding of the technical solution of the present invention to those skilled in the art. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention belong to the protection scope of the present invention.
Unless specifically stated otherwise, technical or scientific terms used herein should be defined in the general sense as understood by one of ordinary skill in the art to which this invention belongs. The use of "including" or "comprising" and the like in the present invention is not intended to limit the shape, number, step, action, operation, component, original and/or group thereof referred to, nor exclude the presence or addition of one or more other different shapes, numbers, steps, actions, operations, components, original and/or group thereof. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or order of the indicated features.
As shown in fig. 1 and 2, the present invention provides a method S100 for cooperatively preparing chlorinated paraffin and polyaluminum chloride flocculant, which specifically includes the following steps S110 to S140:
s110, performing first low-temperature plasma treatment on the chlorine and paraffin oil to obtain a chlorowax primary product and first tail gas.
Specifically, under the normal temperature environment, chlorine and paraffin oil are directly and continuously added into a first-stage low-temperature plasma irradiation reactor, and the first-stage low-temperature plasma irradiation reactor is used for processing to generate a chlorowax primary product and first tail gas.
In some preferred embodimentsIn the examples, the volume of chlorine (Nm 3 ) And the volume of paraffin oil (m 3 ) The proportion range is 450-550:1.
If the volume of chlorine (Nm) 3 ) And the volume of paraffin oil (m 3 ) The ratio is lower than 450:1, the generated chlorine free radical in the low-temperature plasma irradiation process is reduced, and the paraffin oil is easy to be insufficiently chlorinated; if the volume of chlorine (Nm) 3 ) And the volume of paraffin oil (m 3 ) The ratio of chlorine to hypochlorite is higher than 550:1, and the yield of hypochlorite is increased, so that the yield of impurities is increased easily.
In other preferred embodiments, the first low temperature plasma treatment has an applied voltage in the range of 25kV to 125kV.
If the action voltage range of the first low-temperature plasma treatment is lower than 25kV, the ionization and dissociation of chlorine and hydrogen chloride in a discharge channel are insufficient, the reaction of chlorine free radicals and chlorinated paraffin is insufficient, the generation inhibition of hypochlorite is weakened, and the dehydrogenation capability of paraffin oil is reduced; if the action voltage range of the first low-temperature plasma treatment is higher than 125kV, the chlorine and the hydrogen chloride are easy to ionize and dissociate in the discharge channel, and the electron beam bombardment is too intense, the discharge channel releases a large amount of heat to generate a large amount of water vapor, and the water vapor generates hydroxyl free radicals in the discharge channel to destroy the molecular structure of paraffin oil, so that the reduction of the chlorinated paraffin oil is caused.
It should be noted that the first tail gas generally includes at least one of organic matter, water vapor, chlorine gas, and hydrogen chloride.
The invention applies the low-temperature plasma irradiation technology to the preparation of chlorinated paraffin for the first time, in the primary low-temperature plasma irradiation reactor, chlorine gas is ionized and dissociated in a discharge channel to generate chlorine free radicals, and the chlorine free radicals can react with paraffin oil quickly to generate chlorinated paraffin and hydrogen chloride gas. The hydrogen chloride gas can be continuously ionized and dissociated in the discharge channel to generate chlorine free radicals and hydrogen free radicals, the chlorine free radicals can continuously participate in the reaction of chlorinated paraffin, and the hydrogen free radicals can shield the influence of water vapor contained in the chlorine gas on the chlorine and inhibit the generation of hypochlorite, so that the reaction of hypochlorite and paraffin oil to generate impurities is avoided. The high-energy electron beam released in the low-temperature plasma discharge channel bombards the surface of the paraffin oil to promote the dehydrogenation of the paraffin oil, thereby accelerating the reaction process of the paraffin oil and chlorine free radicals and improving the reaction efficiency.
The embodiment is based on low-temperature plasma treatment, and can be carried out only at normal temperature without heating, so that the formed chlorowax primary product has good stability, and a stabilizer is not needed to be added in the subsequent degassing treatment.
S120, degassing the chloroparaffin primary product to obtain chlorinated paraffin and second tail gas.
Specifically, the initial product of the chlorowax is added into a chlorowax degassing kettle for reaction, unreacted chlorine gas and packed hydrogen chloride gas which are removed by heating are converted into a chloroparaffin-52 product, namely, the second tail gas generated by the chlorowax degassing kettle also comprises at least one of oily organic matters, water vapor, chlorine gas and hydrogen chloride.
The chlorinated paraffin obtained in the embodiment has a chlorine content ranging from 51% to 53% and a viscosity ranging from 150mPa.s to 250mPa.s, and meets the corresponding product quality standard.
S130, treating the first tail gas and/or the second tail gas and the aluminum source slurry by using low-temperature plasma for the second time to obtain polyaluminum chloride mixed slurry.
Specifically, mixing an aluminum source material with 0.5-5.5M sodium hydroxide solution, and stirring for 0.5-1.5 h to obtain aluminum source slurry. Continuously adding the aluminum source slurry into a secondary low-temperature plasma irradiation reactor, and simultaneously introducing the first tail gas generated by the primary low-temperature plasma irradiation reactor and the second tail gas generated by the chlorowax degassing kettle into the secondary low-temperature plasma irradiation reactor to generate polyaluminium chloride mixed slurry.
In some preferred embodiments, the second low temperature plasma treatment has an applied voltage in the range of 5kV to 75kV.
If the action voltage range of the second low-temperature plasma treatment is less than 5kV, the mineralization of oily organic substances in the tail gas is insufficient, the tail gas components cannot be effectively ionized and dissociated, the dissolution and the reaction of the aluminum source material are insufficient, and the generation amount of polyaluminium chloride is easy to reduce; if the action voltage range of the second low-temperature plasma treatment is more than 75kV, the electron beam bombardment is too strong, the excessive release is carried out, the aluminum source slurry is easy to be dried, and the process control and the reaction are not facilitated.
The aluminum source material comprises any one or more of calcium aluminate, aluminum hydroxide and bauxite, and the raw materials are conventional aluminum-containing materials, so that the aluminum source material is easy to obtain and low in cost.
The oily organic substances in the tail gas of the embodiment can be mineralized into carbon dioxide and water in the secondary low-temperature plasma irradiation reactor, and water vapor, chlorine and hydrogen chloride in the tail gas are subjected to electrodeionization to generate chlorine radicals, hydroxyl radicals and hydrogen radicals. The high-energy electron beam released in the discharge channel bombards the surface of the aluminum source material, so that the dissolution of the aluminum source material can be accelerated. And then, the generated chlorine radicals, hydroxyl radicals and hydrogen radicals react with the aluminum source material to induce the hydrolysis polymerization of the aluminum source material to generate the polyaluminum chloride.
The embodiment can comprehensively utilize the tail gas, and further react the tail gas with the aluminum source slurry to generate the polyaluminium chloride flocculant so as to realize the synergistic reaction, simplify the reaction process, reduce the discharge of waste and improve the resource utilization rate.
And S140, centrifuging and drying the polyaluminium chloride mixed slurry to obtain the polyaluminium chloride flocculant.
Specifically, the polyaluminum chloride mixed slurry is centrifuged to obtain a polyaluminum chloride solution, and then the polyaluminum chloride solution is introduced into a dryer for drying to obtain the polyaluminum chloride flocculant.
The basicity range of the polyaluminum chloride flocculant obtained by the embodiment is 30% -95%, and the mass fraction of alumina in the polyaluminum chloride flocculant is more than 28%, so that the quality standard of the corresponding product is met.
The method of synergistically preparing chlorinated paraffin and polyaluminum chloride flocculants will be further described in connection with several specific examples:
example 1
The example takes the influence of different ratios of chlorine volume and paraffin oil volume on the quality of the prepared chlorinated paraffin and polyaluminum chloride products as an example, and a system for preparing the chlorinated paraffin and polyaluminum chloride flocculant in a synergic mode mainly comprises a primary low-temperature plasma irradiation reactor, a secondary low-temperature plasma irradiation reactor, a chlorinated paraffin degassing kettle and a dryer, and the chlorinated paraffin and polyaluminum chloride flocculant is prepared based on the system in a synergic mode.
The preparation process comprises the following steps:
s1, directly adding chlorine and paraffin oil into a primary low-temperature plasma irradiation reactor continuously in a normal temperature environment, and generating a chlorowax primary product and tail gas by the primary low-temperature plasma irradiation reactor.
Wherein the reaction in the primary low temperature plasma irradiation reactor, chlorine volume (Nm 3 ) With paraffin oil (m) 3 ) The volume ratios are 450:1, 475:1, 500:1, 525:1 and 550:1 respectively, and the irradiation voltage of the low-temperature plasma is 25kV.
S2, mixing an aluminum source material with a 0.5M sodium hydroxide solution, and stirring for 0.5 hour to obtain an aluminum source slurry, wherein the aluminum source material can be calcium aluminate, aluminum hydroxide or bauxite.
And adding the initial product of the chloroparaffin into a chloroparaffin degassing kettle to react to generate a chloroparaffin-52 product and chloroparaffin degassing kettle tail gas.
S3, continuously adding the aluminum source slurry into a secondary low-temperature plasma irradiation reactor, and simultaneously introducing tail gas generated by the primary low-temperature plasma irradiation reactor and tail gas of the chlorowax degassing kettle into the secondary low-temperature plasma irradiation reactor to generate polyaluminium chloride mixed slurry.
Wherein, the reaction in the secondary low-temperature plasma irradiation reactor has a low-temperature plasma irradiation action voltage of 5kV.
And S4, centrifuging the polyaluminum chloride mixed slurry to obtain a polyaluminum chloride solution, and then introducing the polyaluminum chloride solution into a dryer for drying to obtain the polyaluminum chloride flocculant.
Further, this embodiment also detects chlorinated paraffin and polyaluminum chloride flocculant, specifically including: and (3) measuring the chlorine content of the chlorinated paraffin, measuring the viscosity of the chlorinated paraffin, measuring the basicity of the polyaluminum chloride and measuring the mass fraction of the polyaluminum chloride alumina.
Wherein, the chlorine content of the chlorinated paraffin is measured according to the method for measuring the chlorine content of the chlorinated paraffin (GB-1679). Chlorinated paraffin viscosity measurements were carried out according to the "determination of plasticizer kinematic viscosity" method (GB-1660). Polyaluminum chloride basicity was determined according to water treatment polyaluminum chloride (GBT-22627). The mass fraction of polyaluminum chloride alumina is determined according to the water treatment agent polyaluminum chloride (GBT-22627).
TABLE 1 influence of the ratio of chlorine volume to paraffin oil volume on the quality of the chlorinated paraffin and polyaluminum chloride products prepared
As can be seen from Table 1, the chlorine volume (Nm 3 ) With paraffin oil (m) 3 ) In the first-stage low-temperature plasma irradiation reactor, chlorine gas is ionized and dissociated in a discharge channel to generate chlorine free radicals, the chlorine free radicals can react with paraffin oil quickly to generate chlorinated paraffin and hydrogen chloride gas, and the hydrogen chloride gas can be ionized and dissociated continuously in the discharge channel to generate chlorine free radicals and hydrogen free radicals. The chlorine free radical can continuously participate in the reaction of chlorinated paraffin, and the hydrogen free radical can shield the influence of water vapor contained in the chlorine to chlorine and inhibit the generation of hypochlorite, thereby avoiding the generation of impurities by the reaction of hypochlorite and paraffin oil. The high-energy electron beam released in the low-temperature plasma discharge channel bombards the surface of the paraffin oil to promote the dehydrogenation of the paraffin oil, thereby accelerating the reaction process of the paraffin oil and chlorine free radicals. The water vapor, chlorine and hydrogen chloride in the tail gas are electrolyzed and dissociated to generate chlorine free radicals, hydroxyl free radicals and hydrogen free radicals. The generated chlorine free radicals, hydroxyl free radicals and hydrogen free radicals react with the aluminum source material to induce the aluminum source material to generate hydrolysis polymerization to generate polyaluminum chloride.
The chlorinated paraffin prepared by the embodiment has chlorine content of 51-53%, chlorinated paraffin viscosity of 150-250 mPa.s, polyaluminum chloride basicity of 30-95%, and mass fraction of aluminum oxide in polyaluminum chloride of more than 28%, and meets the product quality requirement.
Example 2
The example takes the influence of the primary low-temperature plasma irradiation action voltage on the quality of the prepared chlorinated paraffin and polyaluminum chloride products as an example, and a system for preparing the chlorinated paraffin and polyaluminum chloride flocculant in a synergic mode mainly comprises a primary low-temperature plasma irradiation reactor, a secondary low-temperature plasma irradiation reactor, a chlorinated paraffin degassing kettle and a dryer, and the chlorinated paraffin and polyaluminum chloride flocculant is prepared based on the system in a synergic mode.
The preparation process comprises the following steps:
s1, directly adding chlorine and paraffin oil into a primary low-temperature plasma irradiation reactor continuously in a normal temperature environment, and generating a chlorowax primary product and tail gas by the primary low-temperature plasma irradiation reactor.
Wherein the reaction in the primary low temperature plasma irradiation reactor, chlorine volume (Nm 3 ) With paraffin oil (m) 3 ) The volume ratio is 500:1, and the irradiation action voltages of the low-temperature plasmas are 25kV, 50kV, 75kV, 100kV and 125kV respectively.
S2, mixing an aluminum source material with a 3M sodium hydroxide solution, and stirring for 1 hour to obtain aluminum source slurry, wherein the aluminum source material can be calcium aluminate, aluminum hydroxide or bauxite.
And adding the initial product of the chloroparaffin into a chloroparaffin degassing kettle to react to generate a chloroparaffin-52 product and chloroparaffin degassing kettle tail gas.
S3, continuously adding the aluminum source slurry into a secondary low-temperature plasma irradiation reactor, and simultaneously introducing tail gas generated by the primary low-temperature plasma irradiation reactor and tail gas of the chlorowax degassing kettle into the secondary low-temperature plasma irradiation reactor to generate polyaluminium chloride mixed slurry.
Wherein, the reaction in the secondary low-temperature plasma irradiation reactor, the low-temperature plasma irradiation action voltage is 40kV.
And S4, centrifuging the polyaluminum chloride mixed slurry to obtain a polyaluminum chloride solution, and then introducing the polyaluminum chloride solution into a dryer for drying to obtain the polyaluminum chloride flocculant.
Further, in this example, the method for measuring chlorinated paraffin chlorine content, chlorinated paraffin viscosity, polyaluminum chloride basicity and polyaluminum chloride alumina mass fraction was the same as that of example 1.
TABLE 2 influence of the first-order Low temperature plasma irradiation action Voltage on the quality of the chlorinated Paraffin and polyaluminum chloride products prepared
As can be seen from Table 2, when the primary low temperature plasma irradiation voltage is 25kV to 125kV, in the primary low temperature plasma irradiation reactor, chlorine gas is ionized and dissociated in the discharge channel to generate chlorine free radicals, and the chlorine free radicals can react with paraffin oil rapidly to generate chlorinated paraffin and hydrogen chloride gas. And the hydrogen chloride gas can continue to ionize and dissociate in the discharge channel to generate chlorine radicals and hydrogen radicals. The chlorine free radical can continuously participate in the reaction of chlorinated paraffin, and the hydrogen free radical can shield the influence of water vapor contained in the chlorine to chlorine and inhibit the generation of hypochlorite, thereby avoiding the generation of impurities by the reaction of hypochlorite and paraffin oil. The high-energy electron beam released in the low-temperature plasma discharge channel bombards the surface of the paraffin oil to promote the dehydrogenation of the paraffin oil, thereby accelerating the reaction process of the paraffin oil and chlorine free radicals.
The chlorinated paraffin prepared by the embodiment has chlorine content of 51-53%, chlorinated paraffin viscosity of 150-250 mPa.s, polyaluminum chloride basicity of 30-95%, and mass fraction of aluminum oxide in polyaluminum chloride of more than 28%, and meets the product quality requirement.
Example 3
The example uses the influence of the second-level low-temperature plasma irradiation action voltage on the quality of the prepared chlorinated paraffin and polyaluminum chloride products as an example, and a system for cooperatively preparing the chlorinated paraffin and polyaluminum chloride flocculant mainly comprises a first-level low-temperature plasma irradiation reactor, a second-level low-temperature plasma irradiation reactor, a chlorinated paraffin degassing kettle and a dryer, and the chlorinated paraffin and polyaluminum chloride flocculant is prepared cooperatively based on the system.
The preparation process comprises the following steps:
s1, directly adding chlorine and paraffin oil into a primary low-temperature plasma irradiation reactor continuously in a normal temperature environment, and generating a chlorowax primary product and tail gas by the primary low-temperature plasma irradiation reactor.
Wherein the reaction in the primary low temperature plasma irradiation reactor, chlorine volume (Nm 3 ) With paraffin oil (m) 3 ) The volume ratio is 550:1, and the irradiation action voltage of the low-temperature plasma is 125kV.
S2, mixing an aluminum source material with a 5.5M sodium hydroxide solution, and stirring for 1.5 hours to obtain an aluminum source slurry, wherein the aluminum source material can be calcium aluminate, aluminum hydroxide or bauxite.
And adding the initial product of the chloroparaffin into a chloroparaffin degassing kettle to react to generate a chloroparaffin-52 product and chloroparaffin degassing kettle tail gas.
S3, continuously adding the aluminum source slurry into a secondary low-temperature plasma irradiation reactor, and simultaneously introducing tail gas generated by the primary low-temperature plasma irradiation reactor and tail gas of the chlorowax degassing kettle into the secondary low-temperature plasma irradiation reactor to generate polyaluminium chloride mixed slurry.
Wherein, the reaction in the secondary low-temperature plasma irradiation reactor has the low-temperature plasma irradiation action voltages of 5kV, 22.5kV, 40kV, 57.5kV and 75kV respectively.
And S4, centrifuging the polyaluminum chloride mixed slurry to obtain a polyaluminum chloride solution, and then introducing the polyaluminum chloride solution into a dryer for drying to obtain the polyaluminum chloride flocculant.
Further, in this example, the method for measuring chlorinated paraffin chlorine content, chlorinated paraffin viscosity, polyaluminum chloride basicity and polyaluminum chloride alumina mass fraction was the same as that of example 1.
TABLE 3 influence of the effect voltage of the two-stage low temperature plasma irradiation on the quality of the chlorinated paraffin and polyaluminum chloride products prepared
As can be seen from Table 3, oily organic substances in the tail gas can be mineralized into carbon dioxide and water in the secondary low-temperature plasma irradiation reactor, water vapor, chlorine gas and hydrogen chloride in the tail gas are electrolyzed to generate chlorine free radicals, hydroxyl free radicals and hydrogen free radicals, and high-energy electron beams released in the discharge channel bombard the surface of the aluminum source material, so that the dissolution of the aluminum source material can be accelerated. The chlorine free radical, the hydroxyl free radical and the hydrogen free radical react with the aluminum source material to induce the aluminum source material to generate the polyaluminum chloride through hydrolytic polymerization.
The chlorinated paraffin prepared by the embodiment has chlorine content of 51-53%, chlorinated paraffin viscosity of 150-250 mPa.s, polyaluminum chloride basicity of 30-95%, and mass fraction of aluminum oxide in polyaluminum chloride of more than 28%, and meets the product quality requirement.
The invention provides a method for preparing chlorinated paraffin and polyaluminum chloride flocculant in a synergistic way, which has the following beneficial effects:
firstly, the invention utilizes the low-temperature plasma technology to cooperate with the chlorinated paraffin and the polyaluminium chloride flocculant, realizes the full quantitative utilization of raw materials, obtains a target product without generating three wastes, has simple preparation process and realizes the comprehensive utilization of resources;
secondly, in the preparation method, the reaction of chlorine and paraffin oil is carried out at normal temperature, and additional heating is not needed;
thirdly, the chlorowax primary product prepared by the invention does not need to be added with a stabilizer in the degassing process;
fourth, the tail gas produced in the preparation process of the invention can be used as a raw material for producing the polyaluminium chloride flocculant, so that the resource utilization rate of the tail gas is effectively improved, and the emission of waste is reduced;
fifth, the chlorinated paraffin-52 product and the polyaluminum chloride product obtained by the invention meet the corresponding product quality standards.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Claims (7)
1. The method for preparing the chlorinated paraffin and the polyaluminum chloride flocculant in a synergic manner is characterized by comprising the following steps of:
the chlorine and paraffin oil are treated by low-temperature plasma for the first time to obtain a chlorowax primary product and first tail gas; the volume ratio of the chlorine to the paraffin oil is 450-550:1, and the action voltage of the first low-temperature plasma treatment is 25-125 kV;
the chloroparaffin primary product is subjected to degassing treatment to obtain chlorinated paraffin and second tail gas;
the first tail gas and/or the second tail gas and the aluminum source slurry are subjected to a second low-temperature plasma treatment to obtain polyaluminum chloride mixed slurry; the action voltage range of the second low-temperature plasma treatment is 5 kV-75 kV;
and centrifuging and drying the polyaluminium chloride mixed slurry to obtain the polyaluminium chloride flocculant.
2. The method of claim 1, wherein the aluminum source slurry is formed by a method comprising:
and mixing the aluminum source material with a sodium hydroxide solution, and stirring for 0.5-1.5 h to obtain aluminum source slurry.
3. The method of claim 2, wherein the aluminum source material comprises one or more of calcium aluminate, aluminum hydroxide, bauxite.
4. The method of claim 1, wherein the first tail gas and the second tail gas each comprise at least one of organics, moisture, chlorine, hydrogen chloride.
5. The method of claim 1, wherein the chlorinated paraffin is chlorinated paraffin-52.
6. The method according to claim 1, wherein the chlorinated paraffin has a chlorine content ranging from 51% to 53%, and the chlorinated paraffin has a viscosity ranging from 150mpa.s to 250mpa.s.
7. The method of claim 1, wherein the basicity of the polyaluminum chloride flocculant is in the range of 30% -95%, and the mass fraction of alumina in the polyaluminum chloride flocculant is greater than 28%.
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| KR20160109440A (en) * | 2015-03-11 | 2016-09-21 | (주)한청알에프 | Manufacturing method of high purity alumina using polyaluminium chloride |
| WO2017018090A1 (en) * | 2015-07-30 | 2017-02-02 | 株式会社トクヤマ | Method for producing higher-order chloroalkane |
| CN108315054A (en) * | 2018-02-12 | 2018-07-24 | 丹阳市助剂化工厂有限公司 | Chlorinated paraffin continuous production processes |
| CN110699115A (en) * | 2019-10-21 | 2020-01-17 | 扬州科力化工有限公司 | Chlorinated paraffin production process capable of improving utilization rate of raw material resources |
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