WO2017206927A1 - 一种耐腐蚀的金属氯化反应釜 - Google Patents

一种耐腐蚀的金属氯化反应釜 Download PDF

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WO2017206927A1
WO2017206927A1 PCT/CN2017/086828 CN2017086828W WO2017206927A1 WO 2017206927 A1 WO2017206927 A1 WO 2017206927A1 CN 2017086828 W CN2017086828 W CN 2017086828W WO 2017206927 A1 WO2017206927 A1 WO 2017206927A1
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layer
zirconium
titanium
gas
liquid phase
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PCT/CN2017/086828
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English (en)
French (fr)
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赵东日
路恩斌
徐峰
边增和
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山东日科化学股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0073—Sealings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0277—Metal based
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/194—Details relating to the geometry of the reactor round
    • B01J2219/1947—Details relating to the geometry of the reactor round oval or ellipsoidal

Definitions

  • the invention relates to the technical field of chemical machinery, in particular to a metal chlorination reactor.
  • the reactors used in the chlorination reaction were all enamel reactors.
  • the advantages of ordinary enamel reactors are resistance to hydrochloric acid and chloride ions, but the disadvantages are also obvious:
  • All chlorination reactions are exothermic reactions, generally above 100 degrees Celsius, and the enamel kettle is due to the carbon of the kettle body.
  • the thermal expansion coefficients of the steel and bismuth glass layers are very different, so it is suitable for the constant temperature reaction. In the chlorination reaction where the temperature changes drastically and the variation range is large, the ruthenium glass layer is easily destroyed.
  • Second, the glass-lined kettle The agitating shaft can only be fixed at the upper end of the reaction vessel, and the lower end cannot be fixed, so the stirring strength is low and the mixing ability is poor.
  • the chlorination reaction is generally a three-phase reaction of gas, solid and water. Only the chlorine gas of the gas phase and the chloride of the solid phase can be dispersed in water, and the chlorination reaction may occur. The more uniform the dispersion, the more the reaction speed Faster, the shorter the reaction time, the higher the efficiency of the reaction, and the more uniform the chlorination degree of the chloride, but the stirring of the enamel kettle can only be fixed at the upper end of the reaction vessel, the stirring ability is poor, the mixing ability is low, the chlorine gas is Chloride can not be uniformly mixed in water, so the reaction rate is slow, the reaction time is long, the chlorination degree of the surface and core part of the chloride is very different and uneven; the enamel kettle is inconvenient to repair, afraid of collision, easy bumping Explosive porcelain; easy to damage during use, the tool in the process is easy to cause damage to the kettle body; there is no support at the bottom of the stirring shaft, the design speed is low, generally not higher than 100 rev / min, the material mixing
  • the technical problem to be solved by the invention is that, in view of the deficiencies of the prior art, a metal chlorination reaction kettle with convenient maintenance, long service life, uniform stirring and mixing, short reaction time and high efficiency, high efficiency and corrosion resistance is provided.
  • the technical solution of the present invention is:
  • a high-efficiency, high-efficiency, corrosion-resistant metal chlorination reactor comprising a kettle body, the kettle body comprising an upper head, a cylinder body and a lower head, wherein the kettle body is provided with a stirring shaft;
  • the cylinder comprises an upper gas-liquid interface zone and a lower liquid phase zone, the agitator shaft comprising an upper shaft corresponding to the upper head, a gas-liquid interface zone, a liquid phase zone, a gas-liquid interface axis and a liquid Phase axis
  • the gas-liquid interface zone comprises a tantalum layer, a zirconium layer, a titanium layer and a carbon steel layer in order from the inside to the outside;
  • the liquid phase zone and the lower head include a zirconium layer, a titanium layer and a carbon steel layer in order from the inside to the outside;
  • the gas-liquid interface axis comprises a titanium alloy axis, a zirconium layer and a ruthenium surface layer in sequence;
  • the liquid phase axis comprises a titanium alloy axis and a zirconium surface layer.
  • the upper head includes a titanium palladium alloy layer and a carbon steel layer from the inside to the outside;
  • the upper shaft of the stirring shaft includes a titanium alloy axis and a titanium palladium alloy skin layer.
  • the stirring shaft is provided with a zirconium fixing seat at the bottom of the kettle body.
  • each set of stirring blades includes at least four zirconium stirring blades.
  • three sets of stirring blades are arranged on the upper and lower sides of the stirring shaft, and the number of the stirring blades of each group is four, six, and six pieces from top to bottom.
  • the kettle body is provided with a zirconium baffle on the inner wall of the kettle body, and the zirconium baffle is disposed obliquely with the inner wall of the kettle body, and the inclined direction is opposite to the stirring direction of the stirring shaft.
  • the zirconium baffle is provided with four pieces, and the zirconium baffle is provided with a plurality of folded plates on the upper and lower sides, and the other ends of the plurality of folded plates are fixedly connected to the inner wall of the kettle.
  • the gas-liquid junction zone and the liquid phase zone have a zirconium layer as a welding layer, and a weld seam between the gas-liquid junction zone and the liquid phase zone is a zirconium weld;
  • the gas-liquid interface axis and The liquid phase axis has a zirconium layer as a solder layer, and the weld between the gas-liquid interface axis and the liquid phase axis is a zirconium weld.
  • the thickness of the titanium-palladium alloy layer of the upper head is 0.5-4 mm; the thickness of the bismuth layer, the zirconium layer and the titanium layer of the gas-liquid interface is ⁇ 3 mm, ⁇ 4 mm, ⁇ 3mm; the thickness of the zirconium layer and the titanium layer of the liquid phase region and the lower head are ⁇ 4mm, ⁇ 3mm; the thickness of the titanium-palladium surface layer of the upper shaft of the stirring shaft is ⁇ 4mm; the gas-liquid junction The thickness of the zirconium layer and the enamel layer of the shaft is ⁇ 4 mm, ⁇ 2 mm in order; the thickness of the zirconium surface layer of the liquid phase axis is ⁇ 4 mm.
  • the thickness of the bismuth layer, the zirconium layer and the titanium layer in the gas-liquid interface region are sequentially ⁇ 2 mm, ⁇ 3 mm, ⁇ 2 mm; the zirconium layer and the titanium layer of the liquid phase region and the lower sealing head Thickness in turn ⁇ 3mm, ⁇ 2mm; the thickness of the titanium and palladium surface layer of the upper shaft of the stirring shaft is ⁇ 3mm; the thickness of the zirconium layer and the enamel layer of the gas-liquid interface axis are ⁇ 3mm, ⁇ 1.5mm in sequence;
  • the zirconium surface layer of the phase axis has a thickness of ⁇ 3 mm.
  • the outer wall of the kettle body is further provided with a jacket, and a plurality of baffles are laterally disposed in the jacket, and the plurality of baffles are on the outer wall of the reaction vessel and the inner wall of the jacket.
  • the reactor of the present invention can be used for chlorination in all aqueous phases, and is particularly suitable for chlorination of solid particles such as chlorine and HDPE in the aqueous phase. Compared with the prior art, the reactor of the present invention has the following advantages:
  • the chlorination reaction kettle of the invention is made of metal material, has good mechanical sealing performance, and the sealing material is made of 304 or silicon carbide material, which is safe, stable and corrosion resistant; the tool can not cause damage to the kettle body during use, and the operation will not be correct.
  • the metal kettle body causes damage, the kettle lid switch operation is more convenient, the seal is guaranteed, it is not easy to be damaged, the kettle is easy to clean, and has a greater advantage than the enamel kettle (easy to bump and blast porcelain); and the enamel kettle is convenient to maintain and the maintenance cost is low. Maintenance efficiency is high.
  • the kettle body and the stirring shaft of the present invention are compounded according to the material characteristics and reaction characteristics of the chlorination reaction, and different parts are made of metal materials with different structures, and the upper head includes a titanium-palladium alloy layer (such as TA9) and carbon from the inside to the outside.
  • the steel layer; the corresponding upper shaft includes a titanium alloy (such as Tc4) axis and a titanium palladium alloy (such as TA9) surface layer, titanium palladium resistant to wet chlorine gas and hydrogen chloride gas corrosion.
  • the gas-liquid interface zone of the kettle body comprises a bismuth layer, a zirconium layer, a titanium layer and a carbon steel layer from the inside to the outside; the corresponding gas-liquid interface axis comprises a titanium alloy axis, a zirconium layer and a ruthenium surface in this order.
  • the liquid level fluctuates up and down under the action of stirring, and has both wet chlorine gas and hydrogen chloride gas, and has a high temperature (up to 135 ° C) concentration of about 10% hydrochloric acid.
  • the choice of titanium palladium or zirconium material alone will cause corrosion, so the position of contact with the liquid gas in the present invention is particularly selected from the metal material tantalum layer (such as Ta1), and the carbon steel cannot be explosively composited due to the large difference in thermal deformation, etc., and needs to pass through zirconium.
  • the transition between the two layers of titanium and the titanium layer (such as TA1) requires a zirconium layer (such as Zr702) transition, and then the titanium layer transition between the zirconium layer and the carbon steel.
  • the liquid phase region and the lower head of the kettle body sequentially include a zirconium layer, a titanium layer and a carbon steel layer from the inside to the outside; the corresponding liquid phase axis includes a titanium alloy axis and a zirconium surface layer; the zirconium material can withstand different concentrations at 150 degrees Celsius Hydrochloric acid Eclipse, but because zirconium (such as Zr702) usually has a high oxygen content, it cannot be directly blasted with carbon steel, and titanium is required as a transition layer.
  • the production operator can use it with confidence and will not cause damage to the kettle body; during the temperature rise and fall process, the temperature difference will not cause damage to the metal chlorination kettle, the temperature rise and fall can be easily controlled, and the production process can Accurate execution; the metal chlorination kettle proves that the production efficiency is extremely high and the maintenance is convenient. It is an advanced high-efficiency and high-efficiency process equipment.
  • the metal chloride tank stirring shaft of the invention is provided with a zirconium fixing seat at the bottom of the kettle body, the material is firm, and the design rotation speed can reach 130 rpm, so the material is evenly stirred and the reaction is sufficient, thereby improving the product quality.
  • the metal chloride tank stirring shaft of the invention is composed of a plurality of metal blade (from top to bottom 4-6-6) and a plurality of blades, the stirring effect is further improved, and the material reaction is more sufficient.
  • the metal chlorination kettle is designed with four baffles on the cylinder to make the material agitation more uniform and more complete, and the multiple flaps on the baffle not only further promote the mixing of the material in the axial and radial directions, but also It is convenient for the operation of the kettle, safe and reliable.
  • the gas-liquid interface zone and the liquid phase zone of the kettle body of the invention, the gas-liquid interface axis and the liquid phase axis, the zirconium layer is used as the welding layer, the gas-liquid junction zone and the liquid phase zone, the gas-liquid interface axis and the liquid phase axis.
  • the weld is a zirconium weld and is more resistant to hydrochloric acid corrosion.
  • the present invention selects a metal material of a reasonable thickness.
  • the greater the thickness of the metal layer close to the reaction material the better, but the cost factor and the chlorination reactor are generally used for ten years.
  • the thickness of the titanium-palladium alloy layer of the upper head is 0.5-4 mm; the thickness of the bismuth layer, the zirconium layer and the titanium layer of the gas-liquid interface zone are ⁇ 3 mm, ⁇ 4 mm, ⁇ 3 mm, respectively; The thickness of the zirconium layer and the titanium layer of the region and the lower head are ⁇ 4 mm, ⁇ 3 mm; the thickness of the titanium-palladium surface layer of the upper shaft of the stirring shaft is ⁇ 4 mm; the zirconium layer and the surface layer of the gas-liquid interface axis The thickness of the zirconium surface layer of the liquid phase axis is ⁇ 4 mm in order of thickness ⁇ 4 mm, ⁇ 2 mm.
  • the invention combines the process characteristics of the chlorination reaction in the water phase to design the structure, and avoids the high cost (the Ta1 material is expensive 4000-5000 yuan/KG, and the design minimizes the use amount of the metal ruthenium).
  • the stirring shaft of the invention can be controlled by a variable frequency motor, and the rotation speed can be adjusted according to the process (0-50HZ).
  • FIG. 1 is a schematic structural view of an embodiment of the present invention
  • FIG. 2 is a schematic view showing the structure of a gas body in a gas-liquid junction zone and a liquid phase zone of the present invention.
  • Figure 3 is a cross-sectional view taken along the line A in Figure 1.
  • a high-efficiency, high-efficiency, corrosion-resistant metal chlorination reactor comprises a kettle body 1 including an upper head 11, a cylinder 12 and The lower head 13 is provided with a stirring shaft 2 and a stirring blade 3, and a jacket 16 is arranged on the outer wall of the kettle body, and a plurality of lateral baffles 17 are arranged in the jacket 16 so as to be arranged in the jacket 16 Forming an S-shaped flow passage from bottom to top;
  • the cylinder 12 includes an upper gas-liquid interface zone 14 and a lower liquid phase zone 15, and the agitator shaft 2 includes an upper shaft corresponding to the upper header 11, the gas-liquid interface zone 14, and the liquid phase zone 15. 21.
  • the gas-liquid interface zone 14 of the cylinder 12 is used for contact with the gas phase due to the fluctuation of the liquid surface during the chlorination reaction.
  • the liquid phase region 15 of the barrel 12 being a portion of the barrel for contacting the liquid phase during the chlorination reaction, as understood by those skilled in the art, the gas-liquid junction of the body
  • the upper portion of the zone is substantially only in contact with the gas phase during the reaction, such as contact with the liquid phase for less than 1% of the total reaction time.
  • the stirring shaft 2 is provided with a zirconium fixing seat 4 at the bottom of the kettle body 1 for receiving the lower end of the stirring shaft 2, and the stirring shaft 2 is driven by the variable frequency motor 5; at least the upper and lower sides of the stirring shaft 2 are arranged Three sets of zirconium agitating blades 3, each set of zirconium agitating blades comprising at least four zirconium agitating blades;
  • the kettle body 1 is provided with a zirconium baffle 6 on the inner wall of the kettle body 1, and the zirconium baffle plate 6 is provided with four blocks, and the four zirconium baffles 6 are obliquely disposed with the inner wall of the kettle body 1, and the inclination direction is
  • the agitating shaft 2 is stirred in the opposite direction.
  • the zirconium baffle 6 (that is, the side of the zirconium baffle 6 which is close to the inner wall of the kettle due to the inclination) is laterally disposed with a plurality of flaps 61, and the other end of the plurality of flaps 61 and the kettle body 1
  • the inner wall is fixedly connected.
  • upper and lower means from top to bottom.
  • the hardness test method is in accordance with the national standard GB/T 2411-2008;
  • test method for tensile strength is in accordance with national standard GB/T 1040.1-2006;
  • the conversion rate of the reaction is calculated according to the following formula
  • the reaction conversion ratio (weight of the produced rubber powder / amount of the reactant reactant) ⁇ 100%; wherein when chlorine is the reactant, the amount of chlorine gas is calculated as one-half of the actual amount added.
  • a high-efficiency, high-efficiency, corrosion-resistant metal chlorination reactor comprising a kettle body 1 comprising an upper head 11, a cylinder 12 and a lower head 13, wherein the kettle body 1 is provided Agitating shaft 2 and agitating blade 3, the outer wall of the kettle is provided with a jacket 16, a plurality of lateral baffles 17 are arranged in the jacket 16;
  • the cylinder 12 includes an upper gas-liquid interface zone 14 and a lower liquid phase zone 15, and the agitator shaft 2 includes an upper shaft corresponding to the upper header 11, the gas-liquid interface zone 14, and the liquid phase zone 15. 21, gas and liquid Boundary axis 22 and liquid phase axis 23;
  • the stirring shaft 2 is provided with a zirconium fixing seat 4 at the bottom of the kettle body 1, the stirring shaft 2 is driven by the variable frequency motor 5; three sets of zirconium stirring blades 3 arranged on the stirring shaft 2, three sets of zirconium stirring blades The number is 4, 6, and 6 from top to bottom;
  • the kettle body 1 is provided with a zirconium baffle 6 on the inner wall of the kettle body 1.
  • the zirconium baffle 6 is uniformly disposed four times vertically on the inner wall of the kettle body 1, and the four zirconium baffles 6 and the kettle body 1
  • the inner wall is inclined at an angle, and the direction of inclination is opposite to the stirring direction of the stirring shaft 2.
  • the zirconium baffle 6 is provided with 4-8 folding plates 61 on the upper and lower sides, and the other end of the folding plate 61 is fixedly connected to the inner wall of the kettle body 1.
  • the upper head is a titanium-palladium alloy layer and a carbon steel layer from the inside to the outside (titanium-palladium TA9 ⁇ 3mm+carbon steel composite plate ⁇ 22mm);
  • the gas-liquid interface zone is a bismuth layer, a zirconium layer and a titanium layer from the inside to the outside.
  • the liquid phase zone is zirconium layer, titanium layer and carbon steel layer from the inside to the outside (Zirconium Zr702 ⁇ 3mm+TA1 ⁇ 2mm+carbon steel ⁇ 24mm);
  • the head is composed of a zirconium layer, a titanium layer and a carbon steel layer from the inside to the outside (zirconium Zr702 ⁇ 3mm+TA1 ⁇ 2mm+carbon steel ⁇ 22mm).
  • the upper shaft of the stirring shaft is composed of titanium alloy axis and titanium palladium surface layer (Tc4d120mm+titanium TA9 ⁇ 3mm);
  • the gas-liquid interface axis is titanium alloy axis, zirconium layer and tantalum surface layer (Tc4d120mm+zirconium Zr702 ⁇ 3mm+ ⁇ Ta1 ⁇ 1. 5 mm);
  • the liquid phase axis consists of a titanium alloy axis and a zirconium-palladium surface layer (Tc4d120mm+zirconium Zr702 ⁇ 3mm).
  • Stirring blade material pure zirconium (Zr702 ⁇ 20mm), fixed seat material: pure zirconium (Zr702), baffle material: pure zirconium (Zr702).
  • the jacket material is carbon steel.
  • the gas-liquid junction zone and the liquid phase zone, and the gas-liquid interface axis and the liquid phase axis are both welded with a zirconium layer, between the gas-liquid junction zone and the liquid phase zone, between the gas-liquid junction axis and the liquid phase axis.
  • the weld is a zirconium weld.
  • Example 2 The difference between Example 2 and Example 1 is that the thickness of each part of the sheet differs:
  • the upper head is a titanium-palladium alloy layer and a carbon steel layer (titanium-palladium TA9 ⁇ 2mm+carbon steel composite plate ⁇ 22mm) from the inside to the outside;
  • the gas-liquid interface zone is a bismuth layer, a zirconium layer and a titanium from the inside to the outside.
  • Layer and carbon steel layer ( ⁇ Ta1 ⁇ 1.2mm+Zirconium Zr702 ⁇ 1.5mm+Titanium TA1 ⁇ 1.5mm+carbon steel ⁇ 24mm); the liquid phase zone is zirconium layer, titanium layer and carbon steel layer from inside to outside (Zirconium Zr702 ⁇ 2mm+TA1 ⁇ 1.5mm+ Carbon steel ⁇ 24mm); the lower head is zirconium layer, titanium layer and carbon steel layer from the inside to the outside (zirconium Zr702 ⁇ 2mm+TA1 ⁇ 1.5mm+carbon steel ⁇ 22mm).
  • the upper shaft of the stirring shaft is composed of titanium alloy axis and titanium palladium surface layer (Tc4d120mm+titanium TA9 ⁇ 2mm); the gas-liquid interface axis is titanium alloy axis, zirconium layer and tantalum surface layer (Tc4d120mm+zirconium Zr702 ⁇ 2mm+ ⁇ Ta1 ⁇ 1. 2 mm); the liquid phase axis is composed of a titanium alloy axis and a zirconium-palladium surface layer (Tc4d120m+zirconium Zr702 ⁇ 2mm).
  • Stirring blade material pure zirconium (Zr702 ⁇ 20mm), fixed seat material: pure zirconium (Zr702), baffle material: pure zirconium (Zr702).
  • Example 3 The difference between Example 3 and Example 1 is that the thickness of each part of the sheet differs:
  • the upper head is a titanium-palladium alloy layer and a carbon steel layer (titanium-palladium TA9 ⁇ 1.5mm+carbon steel composite plate ⁇ 22mm) from the inside to the outside;
  • the gas-liquid boundary zone is a bismuth layer and a zirconium layer from the inside to the outside.
  • Titanium layer and carbon steel layer ( ⁇ Ta1 ⁇ 1.2mm+Zirconium Zr702 ⁇ 1.5mm+Titanium TA1 ⁇ 1.5mm+carbon steel ⁇ 24mm); the liquid phase region is zirconium layer, titanium layer and carbon steel layer from inside to outside (Zirconium Zr702 ⁇ 1.5mm +TA1 ⁇ 1.5mm+carbon steel ⁇ 24mm); the lower head is zirconium layer, titanium layer and carbon steel layer from the inside to the outside (zirconium Zr702 ⁇ 1.5mm+TA1 ⁇ 1.5mm+carbon steel ⁇ 22mm).
  • the upper shaft of the stirring shaft is composed of a titanium alloy axis and a titanium-palladium surface layer (Tc4d120mm+titanium TA9 ⁇ 1.6mm);
  • the gas-liquid interface axis is a titanium alloy axis, a zirconium layer and a ruthenium surface layer (Tc4d120mm+zirconium Zr702 ⁇ 2mm+ ⁇ ) Ta1 ⁇ 1.2 mm);
  • the liquid phase axis consists of a titanium alloy axis and a zirconium-palladium surface layer (Tc4d120m+zirconium Zr702 ⁇ 2mm).
  • Stirring blade material pure zirconium (Zr702 ⁇ 20mm), fixed seat material: pure zirconium (Zr702), baffle material: pure zirconium (Zr702).
  • Comparative Example 1 differs from Example 1 in that the thickness of each part of the sheet differs:
  • the upper head is a titanium-palladium alloy layer and a carbon steel layer from the inside to the outside (titanium-palladium TA9 ⁇ 0.3mm+carbon steel composite plate ⁇ 22mm);
  • the gas-liquid boundary zone is a bismuth layer and a zirconium layer from the inside to the outside.
  • Titanium layer and carbon steel layer ( ⁇ Ta1 ⁇ 1.0mm+Zirconium Zr702 ⁇ 1.0mm+Titanium TA1 ⁇ 1.0mm+carbon steel ⁇ 24mm); the liquid phase region is zirconium layer, titanium layer and carbon steel layer from inside to outside (Zirconium Zr702 ⁇ 1.0mm +TA1 ⁇ 1.0mm+carbon steel ⁇ 24mm); the lower head is zirconium layer, titanium layer and carbon steel layer from the inside to the outside (Zirconium Zr702 ⁇ 1.0mm+TA1 ⁇ 1.0mm+carbon steel ⁇ 22mm).
  • the upper shaft of the stirring shaft is composed of titanium alloy axis and titanium palladium surface layer (Tc4d120mm+titanium TA9 ⁇ 1.6mm); the gas-liquid interface axis is titanium alloy axis, zirconium layer and tantalum surface layer (Tc4d120mm+zirconium Zr702 ⁇ 1. 0 mm + ⁇ Ta1 ⁇ 1.0 mm); the liquid phase axis consists of a titanium alloy axis and a zirconium-palladium surface layer (Tc4d120m + zirconium Zr702 ⁇ 2.0 mm).
  • Stirring blade material pure zirconium (Zr702 ⁇ 20mm), fixed seat material: pure zirconium (Zr702), baffle material: pure zirconium (Zr702).
  • Comparative Example 2 differs from Example 1 in that the gas-liquid interface zone is a layer of tantalum, a titanium layer and a carbon steel layer from the inside to the outside ( ⁇ Ta1 ⁇ 1.5mm+titanium TA1 ⁇ 2mm+carbon steel ⁇ 24mm), and the gas-liquid interface axis is in turn It is a titanium alloy axis, a titanium layer and a tantalum layer (Tc4d120mm+titanium TA1 ⁇ + ⁇ Ta1 ⁇ 1.5mm); wherein the gas-liquid interface zone and the liquid phase zone and the gas-liquid interface axis and the liquid phase axis are made of a titanium layer as a solder layer, gas-liquid The weld between the junction zone and the liquid phase zone, the gas-liquid interface axis and the liquid phase axis is a titanium weld.
  • the gas-liquid interface zone is a layer of tantalum, a titanium layer and a carbon steel layer from the inside to the outside ( ⁇ Ta1 ⁇ 1.5mm+tit
  • the reaction kettles of Examples 1-3, Comparative Example 1, and Comparative Example 2 and a common enamel reaction kettle were used for the chlorination reaction test.
  • the test method was as follows: a dispersant, an emulsifier, and then a dispersion medium were added to the reaction vessel, and then added. High-density polyethylene, stirring speed is 125 rpm (where the stirring speed of the enamel reactor is 85 rpm), the concentration of hydrochloric acid in the reaction material is 10wt%, and the temperature of the reaction material is raised to 80-100 °C after stirring.
  • the service life of the reaction vessel of the first embodiment, the second embodiment, the third embodiment, the comparative example 1, and the comparative example 2 and the ordinary enamel reaction kettle were respectively: 11 years and 6 months, and 11 years and more. Ten years and eight months, four years and eight months, four years and one month, three years and nine months.
  • the chlorination reaction experiment of the chlorination reaction vessel of Example 1 was carried out, 0.25 parts of a dispersing agent was added, 0.24 parts of an emulsifier was added, and then water was added to make the total water consumption and all auxiliary raw materials 360 parts, and the stirring speed was adjusted to 125 rpm.
  • the mixture was extruded on an extruder to obtain a PVC sheet product having poor surface gloss and poor plasticization because the chlorine content of the CPE sample 2 was too low, resulting in the unchlorinated HDPE in the CPE sample 2 being impossible.
  • Compatible with PVC, and the presence of HDPE makes the PVC mixture too much lubricant, resulting in poor plasticization.
  • the PVC sheet had a tensile strength of 35 MPa and an elongation at break of 155%.
  • the chlorination reaction of HDPE was carried out by the chlorination reactor in Example 1, and the reaction process was as follows: 0.50 parts of a dispersant, 0.34 parts of an emulsifier, and then water were added to the chlorination reactor. The total water consumption and all auxiliary raw materials are 350 parts, the stirring speed is adjusted to 125 rpm, and then 30 parts of high-density polyethylene is added. After the temperature of the reaction material is raised to 95 ° C under stirring, the introduction is started. For chlorine gas, the rate of chlorine gas is kept at 16 parts/hour, then the temperature is raised to 126 °C while passing chlorine gas, and the temperature rise time is 1 hour. The temperature rise and chlorine gas are simultaneously performed.
  • the temperature is maintained at 126 ° C. Above, the remaining 20 parts of chlorine gas were introduced at a rate of 20 parts per hour. Then, the temperature was maintained at 128-130 ° C for 1 hour, then cooled to below 40 ° C, centrifuged, and dried to obtain a rubber powder having a breaking elongation of 1066%, a hardness of 52.2 HA, and a tensile strength of 9.5 MPa (CPE). Sample 3). The total chlorine passing time of this reaction was 2 hours.
  • the chlorination reaction of HDPE was carried out by using the ordinary enamel reactor sample according to the following method.
  • the process recipe is as follows: Add 0.50 parts of dispersant to the enamel reactor, add 0.34 parts of emulsifier, then add water, make the total water consumption and all auxiliary materials 350 parts, adjust the stirring speed to 85 rpm, and then Add 30 parts of high-density polyethylene, stir the temperature of the reaction material to 95 ° C, start to pass chlorine gas, at the highest 9 parts / hour chlorine flow rate, while heating the chlorine gas to 126 ° C, warming The time was 1.8 hours, and the temperature was raised and the chlorine gas was simultaneously supplied.
  • the chlorine chloride gas of the present invention has a chlorine gas time of 2 hours, and the chlorination time of the enamel reactor is 4.4 hours, indicating that the stirring capacity of the enamel reactor is poor, chlorine gas. It can not be in sufficient contact with HDPE particles, so the reaction speed is slow; while the stirring shaft of the metal reaction vessel of the invention is fixed at both upper and lower ends, the stirring speed is fast (125 rpm), the stirring ability is strong, and the chlorine gas is sufficiently mixed with the HDPE particles.
  • the reaction speed is fast;
  • the second advantage brought by the strong stirring ability is that the HDPE particles are uniformly dispersed in water, dispersed in water in the state of individual particles, and the specific surface area in contact with chlorine gas is large, so as long as the particle diameter is as large
  • the chlorination uniformity of each particle is completely the same, so the elongation of the obtained CPE is high, and the elongation of the modified PVC product is also high.
  • the ordinary enamel kettle is used, and the stirring ability is poor.
  • the HDPE particles in the water cannot be dispersed into a single granular form, but exist in the aggregate state of the particles, especially in the late stage of the reaction, so that the chlorine gas cannot be in full contact with the HDPE particles.
  • the surface of HDPE particles has a part in contact with chlorine gas, a part which is not in contact with chlorine gas, and an HDPE particle which is not in contact with chlorine gas, so the chlorination rate of HDPE is slow, chlorination is uneven, and the obtained CPE has low elongation.
  • the elongation of the modified PVC product is also low.

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Abstract

一种金属氯化反应釜，包括釜体（1），釜体（1）包括上封头（11）、筒体（12）和下封头（13），釜体（1）内设有搅拌轴（2）和搅拌叶片（3）；筒体（12）包括上部的气液交界区（14）和下部的液相区（15），搅拌轴（2）包括与所述上封头（11）、气液交界区（14）、液相区（15）相对应的上轴（21）、气液交界轴（22）和液相轴（23）；上封头（11）由内到外包括钛钯合金层和碳钢层；气液交界区（14）由内到外依次包括钽层、锆层、钛层和碳钢层；液相区（15）和下封头（13）由内到外依次包括锆层、钛层和碳钢层；搅拌轴（2）的上轴（21）包括钛合金轴心和钛钯表层；气液交界轴（22）依次包括钛合金轴心、锆层和钽表层；液相轴（23）包括钛合金轴心和锆表层。

Description

一种高效率、高效能、耐腐蚀的金属氯化反应釜 技术领域
本发明涉及化工机械技术领域，具体涉及一种金属氯化反应釜。
背景技术
一般的说，以水为介质的氯化反应，由于产生大量的盐酸和氯离子，这些盐酸的水溶液和氯离子与普通的不锈钢产生剧烈的腐蚀反应，所以不能使用金属反应釜进行水相中的氯化反应。
在氯化反应中使用的反应釜都是搪瓷反应釜。普通搪瓷反应釜的优点是耐盐酸和氯离子的腐蚀性，但是缺点也很明显：第一，所有的氯化反应都是放热反应，一般都在100摄氏度以上，搪瓷釜由于釜体的碳钢和搪玻璃层的热膨胀系数差异很大，所以适合于恒温反应，在温度剧烈变化、且变化幅度很大的氯化反应中，很容易造成搪玻璃层的破坏；第二，搪玻璃釜的搅拌轴只能固定在反应釜的上端，下端无法固定，所以搅拌强度低、混合能力差。氯化反应一般都是气、固、水的三相反应，只有气相的氯气和固相的被氯化物在水中能分散开，氯化反应才可能发生，两者分散的越均匀，反应速度越快、反应时间越短、反应的效率就越高、同时氯化物的氯化度越均匀，但是由于搪瓷釜的搅拌只能固定在反应釜的上端，搅拌能力差、混合能力低，氯气和被氯化物不能均匀的混合在水中，故反应速度慢、反应时间长、被氯化物的表面和核心部分的氯化度差异很大、不均匀；搪瓷釜维修不方便，怕磕怕碰、容易磕碰爆瓷；使用过程中易损害，使用过程中工器具对釜体极易造成损害；搅拌轴底部没有支座、设计转速低，一般不得高于100转/分，物料混合能力差，搅拌不均匀等缺陷。
发明内容
本发明所要解决的技术问题是：针对现有技术存在的不足，提供一种维修方便、使用寿命长、搅拌混合均匀、反应时间短的高效率、高效能、耐腐蚀的金属氯化反应釜。
为解决上述技术问题，本发明的技术方案是：
一种高效率、高效能、耐腐蚀的金属氯化反应釜，包括釜体，所述釜体包括上封头、筒体和下封头，所述釜体内设有搅拌轴；
所述筒体包括上部的气液交界区和下部的液相区，所述搅拌轴包括与所述上封头、气液交界区、液相区相对应的上轴、气液交界轴和液相轴；
所述气液交界区由内到外依次包括钽层、锆层、钛层和碳钢层；所述液相区和下封头由内到外依次包括锆层、钛层和碳钢层；所述气液交界轴依次包括钛合金轴心、锆层和钽表层；所述液相轴包括钛合金轴心和锆表层。
作为一种改进的技术方案，所述上封头由内到外包括钛钯合金层和碳钢层；所述搅拌轴的上轴包括钛合金轴心和钛钯合金表层。
作为一种改进的技术方案，所述搅拌轴在釜体底部设有锆固定座。
作为一种改进的技术方案，所述搅拌轴上上下设置有至少两组搅拌叶片，每组搅拌叶片包括至少4个锆搅拌叶片。
作为一种优选的技术方案，所述搅拌轴上上下设置有三组搅拌叶片，自上而下每组搅拌叶片的数量为4片、6片、6片。
作为一种改进的技术方案，所述釜体在所述釜体内壁设有锆挡板，所述锆挡板与釜体内壁倾斜设置，且倾斜方向与搅拌轴的搅拌方向相反。
作为一种进一步改进的技术方案，所述锆挡板设置有四块，所述锆挡板上上下横向设置有多个折板，多个折板的另一端与釜体内壁固定连接。
作为一种改进的技术方案，所述气液交界区与液相区以锆层为焊接层，气液交界区与液相区之间的焊缝为锆焊缝；所述气液交界轴与液相轴以锆层为焊接层，气液交界轴与液相轴之间的焊缝为锆焊缝。
作为一种优选的技术方案，所述上封头的钛钯合金层的厚度为0.5～4mm；所述气液交界区的钽层、锆层、钛层的厚度依次为≤3mm、≤4mm、≤3mm；所述液相区和下封头的锆层、钛层的厚度依次为≤4mm、≤3mm；所述搅拌轴的上轴的钛钯表层的厚度为≤4mm；所述气液交界轴的锆层和钽表层的厚度依次为≤4mm、≤2mm；所述液相轴的锆表层的厚度为≤4mm。
作为进一步优选的技术方案，所述气液交界区的钽层、锆层、钛层的厚度依次为≤2mm、≤3mm、≤2mm；所述液相区和下封头的锆层、钛层的厚度依次 为≤3mm、≤2mm；所述搅拌轴的上轴的钛钯表层的厚度为≤3mm；所述气液交界轴的锆层和钽表层的厚度依次为≤3mm、≤1.5mm；所述液相轴的锆表层的厚度为≤3mm。
作为一种改进的技术方案，所述釜体的外壁还设有夹套，所述夹套内横向设有多个挡板，所述的多个挡板在反应釜的外壁和夹套内壁上交错设置，使得夹套里的循环水流呈S状由下至上流动，提高换热效率。
由于采用了上述技术方案，本发明的有益效果是：
本发明的反应釜可以用于所有的水相中的氯化反应，特别的适合于水相中氯气和HDPE等固体颗粒的氯化反应。与现有技术相比，本发明的反应釜具有以下优点：
1、本发明的氯化反应釜材质均选用金属材质，机械密封性能好，密封材料采用304、碳化硅材质，安全稳定耐腐蚀；使用过程中工器具对釜体不能造成损害、操作不会对金属釜体造成损害，釜口盖开关操作更方便，密封有保障，不易损坏，釜内便于清理，比搪瓷釜(容易磕碰爆瓷)有较大优势；且比搪瓷釜维修方便，维修成本低、维修效率高。
2、本发明釜体和搅拌轴根据氯化反应中物料特性和反应特点，不同部位使用不同结构的金属材料复合而成，上封头由内到外包括钛钯合金层(比如TA9)和碳钢层；与之对应的上轴包括钛合金(比如Tc4)轴心和钛钯合金(比如TA9)表层，钛钯耐湿氯气及氯化氢气体腐蚀。
釜体的气液交界区由内到外依次包括钽层、锆层、钛层和碳钢层；与之对应的气液交界轴依次包括钛合金轴心、锆层和钽表层，这一位置的液面在搅拌的作用下上下波动，既有湿氯气及氯化氢气体，又有温度较高(可达135℃)浓度为10％左右的盐酸。单独选择钛钯或锆材均会出现腐蚀，所以与液体气体接触的位置本发明特别选用金属材料钽层(比如Ta1)，钽跟碳钢由于热变形差距大等原因不能爆炸复合，需要经过锆、钛两层材料过渡，钽跟钛层(比如TA1)需要锆层(比如Zr702)过渡，然后锆层与碳钢之间采用钛层过渡。
釜体的液相区和下封头由内到外依次包括锆层、钛层和碳钢层；与之对应的液相轴包括钛合金轴心和锆表层；锆材能耐150摄氏度下不同浓度盐酸的腐 蚀，但是因锆材(比如Zr702)通常氧含量较高，无法与碳钢直接爆炸复合，需有钛作为过渡层。
金属氯化釜在使用过程中，生产操作人员可放心操作使用，不会对釜体造成损害；在升降温过程中，温差不会对金属氯化釜造成损害，升降温容易控制,生产工艺能够准确执行；金属氯化釜通过使用证明生产效率极高，维修方便，是先进的高效率、高效能的工艺设备。
3、本发明的金属氯化釜搅拌轴在釜体底部设有锆固定座，材质坚固，设计转速可以达到130转/分，因此物料搅拌均匀、反应充分，提升了产品质量。
4、本发明的金属氯化釜搅拌轴采用多层金属桨叶(自上而下4-6-6)、多片桨叶组成，搅拌效果进一步提升、物料反应更加充分。
5、金属氯化釜在筒体上设计了四块挡板，使得物料搅拌更加均匀，反应更加充分，且挡板上的多个折板不仅进一步促进了物料在轴线和径向的混合，也便于下釜作业，安全可靠。
6、本发明釜体气液交界区与液相区以及气液交界轴与液相轴以锆层为焊接层，气液交界区与液相区之间、气液交界轴与液相轴的焊缝为锆焊缝，更耐盐酸腐蚀。
7、本发明根据氯化反应特点，选择合理厚度的金属材料，理论上，靠近反应物料的金属层厚度越大越好，但是，并充分考虑成本因素和氯化反应釜一般为十年的使用期限，所述上封头的钛钯合金层的厚度为0.5～4mm；所述气液交界区的钽层、锆层、钛层的厚度依次为≤3mm、≤4mm、≤3mm；所述液相区和下封头的锆层、钛层的厚度依次为≤4mm、≤3mm；所述搅拌轴的上轴的钛钯表层的厚度为≤4mm；所述气液交界轴的锆层和钽表层的厚度依次为≤4mm、≤2mm；所述液相轴的锆表层的厚度为≤4mm。各金属层的厚度低于上述下限厚度，则达不到十年的使用期限，大于以上上限厚度，则增加制造成本。本发明结合水相中氯化反应的工艺特点进行结构设计，并且避免了高昂费用发生(Ta1材价格昂贵4000-5000元/KG，本设计尽量的减少了金属钽的使用量)。
本发明搅拌轴可采用变频电机控制，转速可随工艺调整(0-50HZ)。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明实施例的结构示意图；
图2是本发明气液交界区与液相区的釜体结构示意图。
图3是图1中A向的剖视示意图。
图中，1.釜体；11.上封头；12.筒体；13.下封头；14.气液交界区；15.液相区；16.夹套；17.夹套挡板；2.搅拌轴；21.上轴；22.气液交界轴；23.液相轴；3.搅拌叶片；4.锆固定座；5.变频电机；6.锆挡板；61.折板；7.钽层；8.锆层；9.钛层；10.碳钢层；80.锆焊接缝。
具体实施方式
下面结合附图和实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
如图1和图2和图3共同所示，一种高效率、高效能、耐腐蚀的金属氯化反应釜，包括釜体1，所述釜体1包括上封头11、筒体12和下封头13，所述釜体1内设有搅拌轴2和搅拌叶片3，釜体外壁设有夹套16，夹套16内设有多个横向挡板17，以便在夹套16内由下至上形成S形流动通道；
所述筒体12包括上部的气液交界区14和下部的液相区15，所述搅拌轴2包括与所述上封头11、气液交界区14、液相区15相对应的上轴21、气液交界轴22和液相轴23，即所述上轴21位于上封头11内，所述气液交界轴22位于气液交界区14内，所述液相轴23位于液相区15内；其中，本领域技术人员理解，所述筒体12的气液交界区14是用于在氯化反应过程中由于液面在搅拌所形成的波动作用既会与气相接触又会与液相接触的筒体部分，所述筒体12的液相区15是用于在氯化反应过程中与液相接触的筒体部分，本领域技术人员理解，所述釜体的气液交界区的上方在反应时基本只与气相接触，比如与液相接触时间在总反应时间的1％以下。
所述搅拌轴2在釜体1底部设有锆固定座4，用于承接所述搅拌轴2的下端，所述搅拌轴2由变频电机5带动；在所述搅拌轴2上上下设置的至少三组锆搅拌叶片3，每组锆搅拌叶片包括至少4个锆搅拌叶片；
所述釜体1在所述釜体1内壁设有锆挡板6，所述锆挡板6设置有四块，所述四块锆挡板6与釜体1内壁倾斜设置，且倾斜方向与搅拌轴2的搅拌方向相反。所述锆挡板6上(即所述锆挡板6由于倾斜而靠近所述釜体内壁的一侧上)上下横向设置有多个折板61，多个折板61的另一端与釜体1内壁固定连接。
在本发明中，术语“上下”意为由上至下。
下边结合具体的实施例、比较例和实验例来说明本发明。
氯化反应釜的制作技术规范和标准与表1所示：
表1.氯化釜制作技术规范及标准
Figure PCTCN2017086828-appb-000001
Figure PCTCN2017086828-appb-000002
以下实验例中所有的“份”与“％”均按重量计，除非另有所指。
以下实验例中的检验方法如下所示：
硬度的检验方法按照国标GB/T 2411-2008；
拉伸强度的检验方法按照国标GB/T 1040.1-2006；
分子量的检验方法，分子量分布的检验方法：液相凝胶色谱法；
断裂伸长率的测定：按照国标GB/T 528-2009，GB/T 1040.1-2006；
反应转化率的测定：根据以下公式计算反应的转化率；
反应转化率＝(生成的橡胶粉末的重量/进料反应物的量)×100％；其中氯气为反应物时，氯气的量按实际加入量的二分之一计算。
PVC片材制品的成型温度：C1＝165℃，C2＝175℃，C3＝185℃。
模头温度＝185℃。
挤出机的规格：螺杆：长径比(L/D)＝25，压缩比＝2.5，主机转速＝60转/分。
模头：宽＝100mm，厚＝3mm。
实施例1
一种高效率、高效能、耐腐蚀的金属氯化反应釜，包括釜体1，所述釜体1包括上封头11、筒体12和下封头13，所述釜体1内设有搅拌轴2和搅拌叶片3，釜体外壁设有夹套16，夹套16内设有多个横向挡板17；
所述筒体12包括上部的气液交界区14和下部的液相区15，所述搅拌轴2包括与所述上封头11、气液交界区14、液相区15相对应的上轴21、气液交 界轴22和液相轴23；
所述搅拌轴2在釜体1底部设有锆固定座4，所述搅拌轴2由变频电机5带动；在所述搅拌轴2上上下设置的三组锆搅拌叶片3，三组锆搅拌叶片数量自上至下为4、6、6个；
所述釜体1在所述釜体1内壁设有锆挡板6，所述锆挡板6在釜体1内壁竖向均匀设置有四块，所述四块锆挡板6与釜体1内壁成一定角度倾斜设置，且倾斜方向与搅拌轴2的搅拌方向相反。所述锆挡板6上上下横向设置有4-8个折板61，折板61的另一端与釜体1内壁固定连接。
釜体材质：上封头由内到外为钛钯合金层和碳钢层(钛钯TA9δ3mm+碳钢复合板δ22mm)；所述气液交界区由内到外依次为钽层、锆层、钛层和碳钢层(钽Ta1δ1.5mm+锆Zr702δ3mm+钛TA1δ2mm+碳钢δ24mm)；所述液相区由内到外依次为锆层、钛层和碳钢层(锆Zr702δ3mm+TA1δ2mm+碳钢δ24mm)；下封头由内到外依次为锆层、钛层和碳钢层(锆Zr702δ3mm+TA1δ2mm+碳钢δ22mm)。
搅拌装置材质：搅拌轴的上轴由钛合金轴心和钛钯表层(Tc4d120mm+钛TA9δ3mm)组成；所述气液交界轴依次为钛合金轴心、锆层和钽表层(Tc4d120mm+锆Zr702δ3mm+钽Ta1δ1.5mm)；所述液相轴由钛合金轴心和锆钯表层(Tc4d120mm+锆Zr702δ3mm)组成。搅拌桨叶材质：纯锆(Zr702δ20mm)、固定座材质：纯锆(Zr702)、挡板材质：纯锆(Zr702)。
夹套材质为碳钢。
其中，气液交界区与液相区以及气液交界轴与液相轴焊接时均以锆层为焊接层，气液交界区与液相区之间、气液交界轴与液相轴之间的焊缝为锆焊缝。
实施例2
实施例2与实施例1的不同之处在于各部分板材的厚度有所不同：
釜体材质：上封头由内到外为钛钯合金层和碳钢层(钛钯TA9δ2mm+碳钢复合板δ22mm)；所述气液交界区由内到外依次为钽层、锆层、钛层和碳钢层(钽Ta1δ1.2mm+锆Zr702δ1.5mm+钛TA1δ1.5mm+碳钢δ24mm)；所述液相区由内到外依次为锆层、钛层和碳钢层(锆Zr702δ2mm+TA1δ1.5mm+碳钢 δ24mm)；下封头由内到外依次为锆层、钛层和碳钢层(锆Zr702δ2mm+TA1δ1.5mm+碳钢δ22mm)。
搅拌装置材质：搅拌轴的上轴由钛合金轴心和钛钯表层(Tc4d120mm+钛TA9δ2mm)组成；所述气液交界轴依次为钛合金轴心、锆层和钽表层(Tc4d120mm+锆Zr702δ2mm+钽Ta1δ1.2mm)；所述液相轴由钛合金轴心和锆钯表层(Tc4d120m+锆Zr702δ2mm)组成。搅拌桨叶材质：纯锆(Zr702δ20mm)、固定座材质：纯锆(Zr702)、挡板材质：纯锆(Zr702)。
实施例3
实施例3与实施例1的不同之处在于各部分板材的厚度有所不同：
釜体材质：上封头由内到外为钛钯合金层和碳钢层(钛钯TA9δ1.5mm+碳钢复合板δ22mm)；所述气液交界区由内到外依次为钽层、锆层、钛层和碳钢层(钽Ta1δ1.2mm+锆Zr702δ1.5mm+钛TA1δ1.5mm+碳钢δ24mm)；所述液相区由内到外依次为锆层、钛层和碳钢层(锆Zr702δ1.5mm+TA1δ1.5mm+碳钢δ24mm)；下封头由内到外依次为锆层、钛层和碳钢层(锆Zr702δ1.5mm+TA1δ1.5mm+碳钢δ22mm)。
搅拌装置材质：搅拌轴的上轴由钛合金轴心和钛钯表层(Tc4d120mm+钛TA9δ1.6mm)组成；所述气液交界轴依次为钛合金轴心、锆层和钽表层(Tc4d120mm+锆Zr702δ2mm+钽Ta1δ1.2mm)；所述液相轴由钛合金轴心和锆钯表层(Tc4d120m+锆Zr702δ2mm)组成。搅拌桨叶材质：纯锆(Zr702δ20mm)、固定座材质：纯锆(Zr702)、挡板材质：纯锆(Zr702)。
比较例1
比较例1与实施例1的不同之处在于各部分板材的厚度有所不同：
釜体材质：上封头由内到外为钛钯合金层和碳钢层(钛钯TA9δ0.3mm+碳钢复合板δ22mm)；所述气液交界区由内到外依次为钽层、锆层、钛层和碳钢层(钽Ta1δ1.0mm+锆Zr702δ1.0mm+钛TA1δ1.0mm+碳钢δ24mm)；所述液相区由内到外依次为锆层、钛层和碳钢层(锆Zr702δ1.0mm+TA1δ1.0mm+碳钢δ24mm)；下封头由内到外依次为锆层、钛层和碳钢层(锆Zr702δ1.0mm+TA1δ1.0mm+碳钢δ22mm)。
搅拌装置材质：搅拌轴的上轴由钛合金轴心和钛钯表层(Tc4d120mm+钛TA9δ1.6mm)组成；所述气液交界轴依次为钛合金轴心、锆层和钽表层(Tc4d120mm+锆Zr702δ1.0mm+钽Ta1δ1.0mm)；所述液相轴由钛合金轴心和锆钯表层(Tc4d120m+锆Zr702δ2.0mm)组成。搅拌桨叶材质：纯锆(Zr702δ20mm)、固定座材质：纯锆(Zr702)、挡板材质：纯锆(Zr702)。
比较例2
比较例2与实施例1的不同之处在于所述气液交界区由内到外依次为钽层、钛层和碳钢层(钽Ta1δ1.5mm+钛TA1δ2mm+碳钢δ24mm)，气液交界轴依次为钛合金轴心、钛层和钽表层(Tc4d120mm+钛TA1δ+钽Ta1δ1.5mm)；其中，气液交界区与液相区以及气液交界轴与液相轴以钛层为焊接层，气液交界区与液相区之间、气液交界轴与液相轴的焊缝为钛焊缝。
实验例1
使用实施例1-3、比较例1、比较例2的反应釜以及普通搪瓷反应釜做氯化反应试验，试验方法如下：在反应釜中加入分散剂、乳化剂，然后加入分散介质，再加入高密度聚乙烯，搅拌转速为125转/分(其中搪瓷反应釜的搅拌转速为85转/分)，反应物料中盐酸浓度为10wt％，搅拌下反应物料的温度升高至80-100℃后，开始通入氯气，通入氯气的同时，缓慢升温至120～136℃之间保温反应3小时，然后冷却至40℃，离心干燥得到氯化聚氯乙烯产品。每一次的反应时间为6-8小时，每天生产三到四反应釜。通过生产实践，实施例1、实施例2、实施例3、比较例1、比较例2的反应釜以及普通搪瓷反应釜的使用寿命分别为：11年6个月以上、11年5个月以上、十年八个月、四年八个月、四年一个月、三年九个月。
实验例2
用实施例1的氯化反应釜进行氯化反应实验，加入0.25份分散剂，加入0.24份乳化剂，然后加入水，使总用水量和所有的辅助原料为360份，调整搅拌转速为125转/分，再加入30份的高密度聚乙烯，搅拌下反应物料的温度升高至92℃后，开始通入18份氯气，通氯气的速度保持在18份/小时，然后一边通氯气一边升温至136℃，升温时间为1小时，升温和通氯气同时进 行，在反应温度达到136℃后，保持温度在136℃以上，以每小时18份的速度通入剩余的18份氯气。然后将温度保持在140-142℃之间反应3小时后，冷却至40℃以下，离心，干燥得到断裂伸长率为1166％，硬度为50.4HA、拉伸强度为10.5MPa的橡胶粉末(CPE样品1)
在高速混合器中，加入100份的PVC(中国石油化工公司齐鲁分公司生产的S-1000，平均聚合度为1000)，8份的上述橡胶粉末(CPE样品1)，12份的碳酸钙，5份的二氧化钛，1.3份的甲基锡(锡含量为18％)热稳定剂，1份的硬脂酸钙，0.5份的石蜡(熔点为60℃)，0.5份的聚乙烯蜡(熔点为110℃)，然后开启搅拌，内部升温至120℃，冷却后得到粉末状PVC混合物。将该混合物在挤出机上挤出得到PVC片状制品。评价拉伸强度和断裂伸长率。PVC片材的拉伸强度为33.3MPa,断裂伸长率为175％。
实验例3
向普通搪瓷反应釜中，加入0.25份分散剂，加入0.24份乳化剂，然后加入水，使总用水量和所有的辅助原料为360份，调整搅拌转速为最高极限85转/分，再加入30份高密度聚乙烯，搅拌下反应物料的温度升高至92℃后，开始通入18份氯气，通氯气的速度保持在18份/小时，然后一边通氯气一边升温至136℃，升温时间为1小时，升温和通氯气同时进行，在反应温度达到136℃后，保持温度在136℃以上，以每小时18份的速度通入剩余的18份氯气。在136℃通氯气时，随着反应的进行，水分散液的粘度越来越大，氯气在水中的分散越来越差、反应速度越来越慢，136℃半小时仅通入了6份氯气，然后压力急剧升高到10大气压，这时反应釜的最高容许压力，通氯被迫停止。然后将温度保持在140-142℃之间反应3小时后，冷却至40℃以下，离心，干燥得到断裂伸长率为850％，硬度为61HA、拉伸强度为7.8MPa的橡胶粉末(CPE样品2)
在高速混合器中，加入100份的PVC(中国石油化工公司齐鲁分公司生产的S-1000，平均聚合度为1000)，8份的上述橡胶粉末(CPE样品2)，12份的碳酸钙，5份的二氧化钛，1.3份的甲基锡(锡含量为18％)热稳定剂，1份的硬脂酸钙，0.5份的石蜡(熔点为60℃)，0.5份的聚乙烯蜡(熔点为110℃)， 然后开启搅拌，内部升温至120℃，冷却后得到粉末状PVC混合物。将该混合物在挤出机上挤出得到PVC片状制品，该制品表面光泽度差，塑化不良，原因是CPE样品2的氯含量太低，造成CPE样品2中的未被氯化的HDPE无法与PVC相容，同时HDPE的存在，使得PVC混合物的润滑剂太多，造成了塑化不良。PVC片材的拉伸强度为35MPa,断裂伸长率为155％。
由实验例2和实验例3可以看出：同样的原材料同样的工艺条件，由于反应釜不同得到的CPE的性能截然不同。本发明金属氯化反应釜所得到的CPE的性能远远地超越了普通的搪瓷反应釜。
实验例4
用实施例1中的氯化反应釜按照以下的方法进行了HDPE的氯化反应，反应工艺配方如下：向氯化反应釜中，加入0.50份分散剂，加入0.34份的乳化剂，然后加入水，使总用水量和所有的辅助原料为350份，调整搅拌转速为125转/分，再加入30份的高密度聚乙烯，搅拌下反应物料的温度升高至95℃后，开始通入16份氯气，通氯气的速度保持在16份/小时，然后一边通氯气一边升温至126℃，升温时间为1小时，升温和通氯气同时进行，在反应温度达到126℃后，保持温度在126℃以上，以每小时20份的速度通入剩余的20份氯气。然后将温度保持在128-130℃之间反应1小时后，冷却至40℃以下，离心，干燥得到断裂伸长率为1066％，硬度为52.2HA、拉伸强度为9.5MPa的橡胶粉末(CPE样品3)。本次反应的总的通氯时间为2个小时。
在高速混合器中，加入100份的PVC(中国石油化工公司齐鲁分公司生产的S-1000，平均聚合度为1000)，8份的上述橡胶粉末(CPE样品3)，12份的碳酸钙，5份的二氧化钛，1.3份的甲基锡(锡含量为18％)热稳定剂，1份的硬脂酸钙，0.5份的石蜡(熔点为60℃)，0.5份的聚乙烯蜡(熔点为110℃)，然后开启搅拌，内部升温至120℃，冷却后得到粉末状PVC混合物。将该混合物在挤出机上挤出得到PVC片状制品。评价拉伸强度和断裂伸长率。PVC片材的拉伸强度为40.6MPa,断裂伸长率为171％。
实验例5
用普通的搪瓷反应釜样品按照以下的方法进行了HDPE的氯化反应，反应 工艺配方如下：向搪瓷反应釜中，加入0.50份分散剂，加入0.34份的乳化剂，然后加入水，使总用水量和所有的辅助原料为350份，调整搅拌转速为85转/分，再加入30份的高密度聚乙烯，搅拌下反应物料的温度升高至95℃后，开始通入氯气，在最高的9份/小时的通氯速度下，一边通氯气一边升温至126℃，升温时间为1.8小时，升温和通氯气同时进行，在反应温度达到126℃后，保持温度在126℃以上，以最高7份/小时的速度通入剩余的20份氯气，耗时2.9小时。然后将温度保持在128-130℃之间反应1小时后，冷却至40℃以下，离心，干燥得到断裂伸长率为950％，硬度为57.2HA、拉伸强度为9.4MPa的橡胶粉末(CPE样品4).本次反应的总的通氯时间为4.4个小时。
在高速混合器中，加入100份的PVC(中国石油化工公司齐鲁分公司生产的S-1000，平均聚合度为1000)，8份的上述橡胶粉末(CPE样品4)，12份的碳酸钙，5份的二氧化钛，1.3份的甲基锡(锡含量为18％)热稳定剂，1份的硬脂酸钙，0.5份的石蜡(熔点为60℃)，0.5份的聚乙烯蜡(熔点为110℃)，然后开启搅拌，内部升温至120℃，冷却后得到粉末状PVC混合物。将该混合物在挤出机上挤出得到PVC片状制品。评价拉伸强度和断裂伸长率。PVC片材的拉伸强度为42.7MPa,断裂伸长率为167％。
由实验例4和实验例5可以看出，本发明的金属氯化釜的通氯气的时间为2小时，而搪瓷反应釜的通氯气时间为4.4小时，说明搪瓷反应釜的搅拌能力差，氯气不能与HDPE颗粒充分的接触所以反应速度慢；而本发明的金属反应釜的搅拌轴的上下两端都固定，搅拌速度快(125转/分)，搅拌能力强，氯气与HDPE颗粒充分的混合，所以反应速度快；搅拌能力强带来的第二个优势是，HDPE颗粒在水中分散均匀，以单个颗粒的状态分散在水中，与氯气接触的比表面积大，所以只要颗粒的粒径一样大，每个颗粒的氯化均匀度就完全一致，所以得到的CPE的伸长率高，改性得到的PVC制品的伸长率也高。而使用普通的搪瓷釜，搅拌能力差，水中的HDPE颗粒不能分散成单个的颗粒状，而是以颗粒的聚集态存在，特别是在反应的后期，这样氯气就不能与HDPE颗粒充分的接触，HDPE颗粒的表面有与氯气接触的部分，有不与氯气接触的部分，还有不与氯气接触的HDPE颗粒，所以HDPE的氯化速度慢，氯化不均匀，得到的CPE的伸长率低，改性得到的PVC制品的伸长率也低。

Claims (10)

  1. 一种高效率、高效能、耐腐蚀的金属氯化反应釜，包括釜体，所述釜体包括上封头、筒体和下封头，所述釜体内设有搅拌轴，其特征在于：
    所述筒体包括上部的气液交界区和下部的液相区，所述搅拌轴包括与所述上封头、气液交界区、液相区相对应的上轴、气液交界轴和液相轴；
    所述气液交界区由内到外依次包括钽层、锆层、钛层和碳钢层；所述液相区和下封头由内到外依次包括锆层、钛层和碳钢层；所述气液交界轴依次包括钛合金轴心、锆层和钽表层；所述液相轴包括钛合金轴心和锆表层。
  2. 如权利要求1所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述上封头由内到外包括钛钯合金层和碳钢层；所述搅拌轴的上轴包括钛合金轴心和钛钯表层。
  3. 如权利要求1或2所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述搅拌轴在釜体底部设有锆固定座。
  4. 如权利要求1-3中任一项所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述搅拌轴上上下设置有至少两组搅拌叶片，每组搅拌叶片包括至少4个锆搅拌叶片。
  5. 如权利要求4所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述搅拌轴上上下设置有三组搅拌叶片，自上而下每组搅拌叶片的数量为4片、6片、6片。
  6. 如权利要求1-5中任一项所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述釜体在所述釜体内壁设有锆挡板，所述锆挡板与釜体内壁倾斜设置，且倾斜方向与搅拌轴的搅拌方向相反。
  7. 如权利要求6所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述锆挡板设置有四块，所述锆挡板上上下横向设置有多个折板，多个折板的另一端与釜体内壁固定连接。
  8. 如权利要求1-7中任一项所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述气液交界区与液相区以锆层为焊接层，气液交界区与液相区之间的焊缝为锆焊缝；所述气液交界轴与液相轴以锆层为焊接层，气液交界轴与液相轴之间的焊缝为锆焊缝。
  9. 如权利要求2所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述上封头的钛钯合金层的厚度为0.5～4mm；所述气液交界区的钽层、锆层、钛层的厚度依次为≤3mm、≤4mm、≤3mm；所述液相区和下封头的锆层、钛层的厚度依次为≤4mm、≤3mm；所述搅拌轴的上轴的钛钯表层的厚度为≤4mm；所述气液交界轴的锆层和钽表层的厚度依次为≤4mm、≤2mm；所述液相轴的锆表层的厚度为≤4mm。
  10. 如权利要求9所述的高效率、高效能、耐腐蚀的金属氯化反应釜，其特征在于：所述气液交界区的钽层、锆层、钛层的厚度依次为≤2mm、≤3mm、≤2mm；所述液相区和下封头的锆层、钛层的厚度依次为≤3mm、≤2mm；所述搅拌轴的上轴的钛钯表层的厚度为≤3mm；所述气液交界轴的锆层和钽表层的厚度依次为≤3mm、≤1.5mm；所述液相轴的锆表层的厚度为≤3mm。
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