WO2016192312A1 - 一种加压碳化反应装置 - Google Patents

一种加压碳化反应装置 Download PDF

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WO2016192312A1
WO2016192312A1 PCT/CN2015/094407 CN2015094407W WO2016192312A1 WO 2016192312 A1 WO2016192312 A1 WO 2016192312A1 CN 2015094407 W CN2015094407 W CN 2015094407W WO 2016192312 A1 WO2016192312 A1 WO 2016192312A1
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tank
pressure
high pressure
inlet
outlet
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French (fr)
Inventor
李军
刘群鸿
魏文欣
祝宝
胡晓慧
王宏涛
苏玉忠
洪燕珍
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Xiamen University
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Xiamen University
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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
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • 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
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
    • 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
    • B01J19/24—Stationary reactors without 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
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • 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
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/60—Preparation of carbonates or bicarbonates in general
    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to a device for carbonization reaction, and more particularly to a pressurized carbonization reaction device.
  • High pressure carbonization refers to direct reaction with high pressure carbon dioxide.
  • High pressure carbonization has a wide range of applications, such as the preparation of inorganic materials, some organic reactions.
  • the technology is mainly for inorganic materials, such as the reaction of water glass with carbon dioxide, the reaction of sodium metasilicate and carbon dioxide.
  • Patent CN1597093A proposes a method for preparing amorphous silicon aluminum by carbonization method, and adopting a pH of a carbon dioxide modulation solution in a raw material sodium aluminate The value was calculated by intermittently synthesizing a silicoalumino compound by stirring with carbon dioxide in an atmospheric pressure reactor.
  • Patent CN101618886A Disclosed is an aluminum hydroxide and a preparation method thereof. The sodium metasilicate is used as a raw material, and the carbonization method is a gas phase reaction with a liquid phase surface, that is, a bubbling reaction, and aluminum hydroxide is synthesized in a batch reactor.
  • Patent CN102039195A A method for preparing an alumina carrier is developed, which is also a batch synthesis of an alumina carrier by a bubbling reaction of a carbonization method.
  • Patent CN102039151A A hydrocracking catalyst and a method of preparing the same are disclosed.
  • the catalyst is prepared by carbonization and is hydrothermally treated with amorphous silicon aluminum. Adjust pH to 8 ⁇ 11 by introducing carbon dioxide
  • the catalyst was synthesized by batch operation.
  • These patents use carbon dioxide to mix raw materials or adjust the pH with carbon dioxide under normal pressure in a kettle. Value.
  • the reaction time is long, the degree of mixing of the raw materials is affected by the equipment, and the stability of the product is difficult to ensure.
  • Patent CN102875840A Under certain conditions, sodium silicate solution and pressurized carbon dioxide were obtained in the reaction vessel under the action of surfactant and silane coupling agent to obtain silica, and aged, washed and dried to obtain a highly dispersed silica product.
  • Patent CN102020284A A method for preparing a silica by a high-pressure carbonization reaction coupled with supercritical drying: reacting sodium silicate solution with supercritical or subcritical carbon dioxide under stirring in a high pressure reactor 1 ⁇ 60 In minutes, the product is washed and supercritically dried to give a larger pore volume of silica.
  • Patent CN103086388A proposes reacting a certain concentration of water glass with carbon dioxide in an autoclave, aging 1-3h Finally, washing and drying to obtain high pore volume silica.
  • Patent CN104477924A A method for preparing spherical nano-silica by supercritical carbonization was proposed. Ethanol was added to the sodium silicate solution to stir the reaction under supercritical conditions of carbon dioxide. About a minute, and a silica product is obtained by supercritical drying.
  • the present invention adopts the following technical solutions:
  • a device for pressurizing carbonization reaction Including atomizing gas tank, complex compressor, multiple buffer tank, multiple preheater, pressurized liquid tank, nozzle, raw material tank, carbon dioxide tank, high pressure reactor, crude product tank, raw material pump, complex pressure display, multiple temperatures Control and display tables and complex back pressure valves;
  • the atomizer tank outlet is connected to the first compressor inlet and the first back pressure valve outlet, the first back pressure valve inlet is connected to the first compressor outlet, and is connected to the first buffer tank inlet via the first check valve, first The buffer tank outlet is connected to the first preheater inlet via a second check valve, and the first preheater outlet is connected to the first inlet of the pressurized liquid tank;
  • the raw material tank outlet is connected to the raw material pump inlet, the raw material pump outlet is connected to the second preheater inlet, the second preheater outlet is connected to the second inlet of the pressurized liquid tank, and the pressurized liquid tank outlet is connected to the nozzle inlet through the second check valve, the nozzle The outlet is connected to the first inlet of the high pressure reactor;
  • the carbon dioxide tank outlet is connected to the second compressor inlet and the second back pressure valve outlet, the second back pressure valve inlet is connected to the second compressor outlet, and is connected to the second buffer tank inlet via the third check valve, the second buffer tank The outlet is connected to the third preheater inlet via the fourth check valve, and the third preheater outlet is connected to the second inlet of the high pressure reactor;
  • the outlet of the high pressure reactor is connected to the inlet of the crude product tank via a fifth check valve;
  • the first buffer tank and the second buffer tank are each provided with a pressure display table; the pressurized liquid tank and the high pressure reactor are provided with temperature control and display tables.
  • the method for pressurizing a carbonization reaction comprising the above apparatus for pressurizing carbonization reaction, comprising the steps of:
  • the temperature of the autoclave and the pressurized liquid tank may be from 10 ° C to 100 ° C.
  • the pressure of the high pressure reactor can be 0.1 ⁇ 15.0MPa, and the pressure of the pressurized liquid tank can be 2.0 ⁇ 20.0MPa, to ensure that the pressure of the high pressure reactor is lower than the pressure of the pressurized liquid tank.
  • step 2) The pressure in the pressurized liquid tank is achieved by pumping the liquid material, or by pumping a high pressure inert gas through the first compressor to achieve the desired pressure; the pressure of the high pressure reactor can be pumped through the second compressor to achieve the desired pressure.
  • the pressure of the pressurized liquid tank can be controlled by the first compressor by pumping high pressure inert gas, and the pressure can be 10.0 MPa.
  • the pump pressure is controlled by the second compressor.
  • the pressure of the high pressure reactor can be 4.0 MPa.
  • step 4 the liquid level in the high pressure reactor is controlled by the fifth check valve to continuously and stably discharge the reaction product.
  • the invention has the advantages that the liquid reaction material is atomized into fine droplets under high pressure by an atomizing device under high pressure, and these fine droplets realize rapid and sufficient reaction with high-pressure carbon dioxide.
  • the reaction time is very short, and the whole raw material takes only a few seconds from entering the reaction tank to discharging, which is shorter than the time mentioned in the patent CN201310019808.X, which takes 1 ⁇ 3 hours in the reaction kettle. .
  • the raw material is sufficiently reacted after atomization, and the conversion rate is very high. For example, in the production of high pore volume silica, the conversion rate of the raw material can be stabilized to more than 99%, which exceeds the conversion rate of the currently commercially produced silica process.
  • the invention adopts atomization rapid reaction, does not need to use high-pressure stirring and other devices, does not need large-scale high-pressure equipment, solves the technical problem of high-pressure stirring in the current industry, and solves the problem of large investment in large-scale high-voltage equipment at present. It is expected to greatly promote the application of high-pressure carbonization reaction in current industrial production.
  • the invention has simple process and convenient control, and can realize continuous and large-scale production of carbonization reaction, and the product quality is high quality, stable, energy saving and environmental protection.
  • BJH pore volume > 3.0 cm 3 /g
  • BJH pore size > 20 nm
  • BET ratio With a surface area of >600 cm 2 /g, its transparency, pore volume and specific surface area are superior to those of the current high-end products.
  • FIG. 1 is a schematic view showing the structure of an apparatus for pressurizing a carbonization reaction according to the present invention.
  • an apparatus for pressurizing carbonization reaction includes an atomizing gas tank E-0. , multiple compressors, multiple buffer tanks, multiple preheaters, pressurized liquid tank E-3, nozzle N-1, raw material tank E-5, carbon dioxide tank E-6, high pressure reactor E-9, crude product tank E -10 Raw material pump P-3, multiple pressure display, multiple temperature control and display, multiple back pressure valves and multiple check valves.
  • Atomizer tank E-0 outlet connected to first compressor P-1 inlet and first back pressure valve V-1 return, first back pressure valve V-1
  • the inlet is connected to the outlet of the first compressor P-1, and is connected to the inlet of the first buffer tank E-1 via the first check valve V-2, and the outlet of the first buffer tank E-1 is connected via the second check valve V-3
  • Carbon dioxide tank E-6 outlet connected to second compressor P-2 inlet and second back pressure valve V-5 return, second back pressure valve V-5
  • the inlet is connected to the outlet of the second compressor P-2, and is connected to the second buffer tank E-7 inlet via the third check valve V-6, and the second buffer tank E-7 outlet is connected via the fourth check valve V-7.
  • the high pressure reactor E-9 outlet is connected to the crude product tank E-10 inlet via the fifth check valve V-8.
  • First buffer tank E-1 and second buffer tank E-7 sets the pressure display tables P1 and P2 respectively; the pressurized liquid tank E-3 and the high pressure reactor E-9 set the temperature control and display tables T1 and T2 respectively.
  • the method for pressurizing carbonization reaction, the device using the pressurized carbonization reaction comprising the following steps:
  • the liquid material can be formulated to a concentration of 0.1 ⁇ 4.0mol/L according to the reaction needs. Left and right.
  • the liquid material refers to a solution, suspension containing the reactants, wherein the additive may be added according to the needs of the product.
  • step 2) the temperature of the high pressure reactor E-9 and the pressurized liquid tank E-3 can be set at about 10 ⁇ 100 °C.
  • step 2) the pressure of the high pressure reactor E-9 can be controlled at 0.1 ⁇ 15.0MPa, pressurized liquid tank E-3
  • the pressure can be controlled at 2.0 ⁇ 20.0MPa, and the pressure of the high pressure reactor E-9 is lower than the pressure of the pressurized liquid tank E-3.
  • step 2) it is ensured that there is a certain pressure difference between the pressurized liquid tank E-3 and the high pressure reactor E-9.
  • the pressure in the medium can be achieved by pumping the feedstock pump P-3, or by pumping a high-pressure inert gas (such as nitrogen) through the first compressor P-1 to achieve the required pressure.
  • High pressure reactor E-9 The pressure can be pumped through the second compressor P-2 to the desired pressure.
  • Step 3 In the case, the nozzle is commercially available, and the model size can be appropriately selected according to the scale of the device. Or the atomized raw material liquid can also be realized by atomizing the liquid material by atomizing gas. As by the first compressor P-1 Pumped into high pressure inert gas nitrogen control Pressurized liquid tank E-3 Pressure 10.0MPa, second compressor P-2 Pumped carbon dioxide control High pressure reactor E-9 Pressure 4.0MPa This also allows the liquid material to be atomized well into the high pressure reactor E-9.
  • the stable discharge of the reaction product in step 4) can be controlled by controlling the fifth check valve.
  • E-9 The liquid level in the middle to achieve continuous discharge. It can also be accumulated to a certain liquid level and then intermittently discharged. The liquid level can be determined as needed.
  • Drugs sodium silicate hydrate (National Pharma Group Chemical Reagent Co., Ltd., analytical grade), carbon dioxide (Xiamen Linde gas, purity ⁇ 99.0% ).
  • Preparation self-fitted with 5L 0.25 mol/L sodium silicate solution, preheating temperature controlled at 25 ° C .
  • the autoclave is filled with dilute carbon and stabilized at 4.0 MPa with a carbon dioxide pump or compressor and a pressure regulating device (such as a back pressure valve system) at a temperature of 25 °C.
  • the first step is to maintain the pressure of the pressurized liquid tank at 8.0 MPa, the temperature is controlled at 25 ° C, and the nozzle (500 ⁇ m)
  • the pores are atomized with sodium silicate solution, and the sodium silicate solution is atomized into the high pressure reactor.
  • the second step is continuous discharge from the high pressure reactor (discharge rate is about 1.49 L / min).
  • Post-treatment A small amount of liquid material after the reaction was determined by the method of dropping acid to determine the content of sodium hydrogencarbonate, and the conversion rate of sodium silicate was calculated to be 99.5%.
  • the liquid material after the reaction is washed (no bicarbonate ion), supercritical drying to obtain the product silica, and the performance of the silica material of the product is analyzed by ASAP2020, and the BET specific surface area is 824 m 2 /g, and the BJH pore volume is 4.53 cm. 3 / g, BJH pore size 21.9nm.
  • the performance of the product silica material was analyzed by a Euro-Glass laser particle size analyzer, and the particle diameter D 50 was 17.8 ⁇ m.
  • Drugs sodium silicate hydrate (National Pharma Group Chemical Reagent Co., Ltd., analytical grade), carbon dioxide (Xiamen Linde gas, purity ⁇ 99.0% ).
  • This embodiment 2 is similar to the embodiment 1, except that the pressure of the raw material tank is maintained at 12.0 MPa through the nozzle (180 ⁇ m). The pores are atomized with sodium silicate solution, and the sodium silicate solution is atomized into the high pressure reactor.
  • the analysis showed that the conversion rate of sodium silicate was 99.7 %, the BET specific surface area of the product silica material was 710 m 2 /g, the BJH pore volume was 4.55 cm 3 /g, and the BJH pore size was 27.7 nm.
  • Drugs sodium silicate hydrate (National Pharma Group Chemical Reagent Co., Ltd., analytical grade), carbon dioxide (Xiamen Linde gas, purity ⁇ 99.0% ).
  • This example uses the same procedure as in Example 1, except that: In the first step, the pressure of the raw material tank is maintained at 10.0 MPa through the nozzle ( 500 ⁇ m pores were sprayed with sodium silicate solution, and the sodium silicate solution was atomized into a high pressure reaction vessel.
  • the analysis showed that the conversion rate of sodium silicate was 99.6%, the BET specific surface area of the product silica material was 732 m 2 /g, the BJH pore volume was 5.11 cm 3 /g, and the BJH pore size was 28.9 nm.
  • Drugs sodium silicate hydrate (National Pharma Group Chemical Reagent Co., Ltd., analytical grade), carbon dioxide (Xiamen Linde gas, purity ⁇ 99.0% ).
  • This example uses the same procedure as in Example 1, except that: 5L of 0.75 mol/L sodium silicate solution is provided.
  • Drugs sodium silicate hydrate (National Pharma Group Chemical Reagent Co., Ltd., analytical grade), carbon dioxide (Xiamen Linde gas, purity ⁇ 99.0% ).
  • This example uses the same steps as in Example 1, except that: In the first step, the pressure of the raw material tank is maintained at 12.0 MPa through the nozzle ( 500 ⁇ m pore) atomized sodium silicate solution
  • the analysis showed that the conversion rate of sodium silicate was 99.3 %, the BET specific surface area of the product silica material was 694 m 2 /g, the BJH pore volume was 4.52 cm 3 /g, and the BJH pore diameter was 25.9 nm.
  • Drugs sodium silicate hydrate (National Pharma Group Chemical Reagent Co., Ltd., analytical grade), carbon dioxide (Xiamen Linde gas, purity ⁇ 99.0% ), n-butanol (National Pharmaceutical Group Chemical Reagent Co., Ltd., analytical grade).
  • This example uses the same steps as in Example 1, except that: Self-contained 5L 0.25 mol/L The sodium silicate solution is added with the additive n-butanol.
  • the analysis showed that the conversion rate of sodium silicate was 100%, the BET specific surface area of the product silica material was 820 m 2 /g, the BJH pore volume was 4.53 cm 3 /g, and the BJH pore size was 18.6 nm.
  • Drugs sodium silicate hydrate (National Pharma Group Chemical Reagent Co., Ltd., analytical grade), carbon dioxide (Xiamen Linde gas, purity ⁇ 99.0%), N,N-dimethylformamide (National Pharmaceutical Group Chemical Reagent Co., Ltd., analytical grade).
  • This example uses the same steps as in Example 1, except that: Self-contained 5L 0.25 mol/L The sodium silicate solution was added with the additive N,N-dimethylformamide.
  • Drugs sodium metaaluminate (National Pharmaceutical Group Chemical Reagent Co., Ltd., analytical grade), carbon dioxide (Xiamen Linde gas, purity ⁇ 99.0% ).
  • This example employs the same procedure as in Example 1, except that the reaction raw material is a liquid sodium metaaluminate solution, and the calcined product is ⁇ -Al 2 O 3 .
  • the aluminum oxide product has a BET specific surface area of 89.3 m 2 /g, a BJH pore volume of 0.41 cm 3 /g, and a BJH pore size of 24.8 nm.
  • the apparatus and method for the pressurization carbonization reaction can realize a rapid carbonization reaction under high pressure to realize a continuous reaction (refer to continuous feeding and discharging). Moreover, the conversion rate is high and the product quality is good.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract

一种加压碳化反应的装置及其方法，包括雾化气罐（E-0）、复数压缩机、复数缓冲罐、复数预热器、加压液体罐（E-3）、喷嘴（N-1）、原料罐（E-5）、二氧化碳罐（E-6）、高压反应釜（E-9）、粗产品罐（E-10）、原料泵（P-3）、复数压力显示表、复数温度控制和显示表和复数背压阀。将固体物料溶解在溶剂中，得液体物料储存于原料罐（E-5）内；二氧化碳罐（E-6）中的气体通入高压反应釜（E-9）中，控制高压反应釜（E-9）与加压液体罐（E-3）温度，再用原料泵（P-3）将液体物料泵入加压液体罐（E-3）中，保证加压液体罐（E-3）与高压反应釜（E-9）有压差；开启第二止回阀（V-4），保证高压反应釜（E-9）与加压液体罐（E-3）在稳定压差下，液体物料经喷嘴（N-1）雾化后与高压反应釜（E-9）中的二氧化碳气氛反应；保证高压反应釜（E-9）中的液体物料在相应液位时，打开第五止回阀（V-8），持续出料，得到反应产物。

Description

一种加压碳化反应装置
技术领域
本发明涉及碳化反应的装置，尤其是涉及一种加压碳化反应装置。
背景技术
高压碳化反应是指与高压二氧化碳直接反应。高压碳化反应具有广泛的应用，如制备无机材料、一些有机反应。本技术主要针对无机材料，比如水玻璃与二氧化碳的反应，偏铝酸钠与二氧化碳的反应等。
专利 CN1597093A 提出一种碳化法制备无定型硅铝的方法，在原料铝酸钠中通入二氧化碳调变溶液的 pH 值，在常压反应釜中借助二氧化碳搅拌，实现间歇合成硅铝化合物。专利 CN101618886A 公开了一种氢氧化铝及其制备方法，以偏铝酸钠为原料，采用的碳化法为气相和液相表面反应，即鼓泡反应，在间歇反应釜中合成氢氧化铝。专利 CN102039195A 开发一种氧化铝载体的制备方法，也是采用碳化法的鼓泡反应间歇合成氧化铝载体。专利 CN102039151A 公开了一种加氢裂化催化剂及其制备方法。该催化剂采用碳化法制备并经水热处理的无定型硅铝。通过通入二氧化碳调节 pH 为 8~11 ，采用间歇操作合成催化剂。这几个专利均是在釜中常压下用二氧化碳混合原料或用二氧化碳调节 pH 值。其反应时间较长，原料混合程度受设备影响，产品稳定性难以保证。
专利 CN102875840A 提出一定条件下硅酸钠溶液与加压二氧化碳在反应釜中于表面活性剂、硅烷偶联剂作用下得到二氧化硅，并经老化、洗涤、干燥得到高分散二氧化硅产品。进行专利 CN102020284A 发明了一种高压碳化反应耦合超临界干燥的方法制备二氧化硅：在高压反应釜中搅拌下硅酸钠溶液与超临界或亚临界二氧化碳进行反应 1~60 分钟，产物洗涤、超临界干燥得到较大孔容的二氧化硅。专利 CN103086388A 提出将一定浓度的水玻璃在高压釜中与二氧化碳进行反应、老化 1-3h ，最后洗涤、干燥得到高孔容二氧化硅。专利 CN104477924A 提出了超临界碳化法制备球形纳米二氧化硅的方法，在硅酸钠溶液中添加乙醇，在二氧化碳超临界状态下搅拌反应 20 分钟左右，并通过超临界干燥制得二氧化硅产品。上述方法，以及现有报道的一些文献方法，属于高压气液反应（高压、搅拌或添加剂作用下加大加快二氧化碳在液相中的溶解，从而加快反应），虽然相对常压下气液反应其传质限制得到改善，但在高压下快速搅拌不容易实现，特别是有凝胶生成的情况，从而使得反应在反应器中停留时间加长，反应过程属于间歇反应范畴，其高压下设计使用大反应器投资成本高，规模化生产受阻。
如何打破上述限制，实现高压下快速、连续碳化反应并获得稳定产品已成为业内非常关注的课题。
发明内容
本发明的目的在于提供一种通过喷嘴或细管雾化液体反应物料，与高压二氧化碳充分接触，实现快速碳化反应的一种加压碳化反应的装置。
为实现上述目的，本发明采用如下技术方案：
一种加压碳化反应的装置， 包括雾化气罐、复数压缩机、复数缓冲罐、复数预热器、加压液体罐、喷嘴、原料罐、二氧化碳罐、高压反应釜、粗产品罐、原料泵、复数压力显示表、复数温度控制和显示表和复数背压阀；
雾化器罐出口接第一压缩机入口和第一背压阀回口，第一背压阀入口与第一压缩机出口相连，并经第一止回阀接第一缓冲罐入口，第一缓冲罐出口经第二止回阀接第一预热器入口，第一预热器出口接加压液体罐第一入口；
原料罐出口接原料泵入口，原料泵出口接第二预热器入口，第二预热器出口接加压液体罐第二入口，加压液体罐出口经第二止回阀接喷嘴入口，喷嘴出口接高压反应釜第一入口；
二氧化碳罐出口接第二压缩机入口和第二背压阀回口，第二背压阀入口与第二压缩机出口相连，并经第三止回阀接第二缓冲罐入口，第二缓冲罐出口经第四止回阀接第三预热器入口，第三预热器出口接高压反应釜第二入口；
高压反应釜出口经第五止回阀接粗产品罐入口；
第一缓冲罐和第二缓冲罐均设压力显示表；加压液体罐和高压反应釜均设温度控制和显示表。
所述一种加压碳化反应的方法，采用上述加压碳化反应的装置，包括以下步骤：
1 ）称取固体物料并完全溶解在溶剂中，得到液体物料，液体物料储存于原料罐内，液体物料调配至浓度为 0.1~4.0mol/L ；
2 ）开启设备， 二氧化碳罐中的气体经第二压缩机通入高压反应釜中，控制高压反应釜与加压液体罐的温度，然后再用原料泵将液体物料泵入加压液体罐中，使加压液体罐具有压力，并保证加压液体罐与高压反应釜有压差；
3 ）待 高压反应釜与加压液体罐中的温度、压力稳定后，开启第二止回阀，保证高压反应釜与加压液体罐在稳定的压差下，液体物料经喷嘴雾化后与高压反应釜中的二氧化碳气氛充分接触，快速反应；
4 ）保证 高压反应釜中的液体物料在相应液位时，打开第五止回阀，持续出料，得到反应产物。
步骤 2 ）中， 高压反应釜和加压液体罐温度可为 10 ℃ ~100℃ 。
步骤 2 ）中， 高压反应釜压力可为 0.1~15.0MPa ， 加压液体罐压力可为 2.0~20.0MPa ，保证 高压反应釜的压力低于加压液体罐的压力。
步骤 2 ）中， 加压液体罐中的压力通过泵入液体物料实现，或通过第一压缩机泵入高压惰性气体来达到所需压力；高压反应釜的压力可通过第二压缩机泵入二氧化碳达到所需压力。
步骤 3 ）中，通过第一压缩机泵入高压惰性气体控制 加压液体罐压力可为 10.0MPa ，通过第二压缩机泵入二氧化碳控制 高压反应釜压力可为 4.0MPa 。
步骤 4 ）中，通过第五止回阀控制 高压反应釜中的液位高度，实现反应产物连续稳定排出。
本发明的优点在于：液体反应物料通过高压下的雾化装置雾化成高压下的细小液滴，这些细小液滴与高压二氧化碳实现快速充分反应。（ 1 ）其反应时间非常短，整个原料从进入反应罐到出料最快只需几秒钟，比专利 CN201310019808.X 中提到的在反应釜中要停留 1~3 小时要缩短大量的时间。（ 2 ）原料在雾化后充分反应，其转化率非常高。如在生产高孔容二氧化硅时，原料的转化率可稳定达到 99% 以上，超过目前工业上生产二氧化硅工艺的转化率。（ 3 ）在原料与二氧化碳接触反应中本发明采用雾化快速反应，无需使用高压搅拌等装置，无需大型高压设备，解决目前工业中高压搅拌的技术难题，解决目前大型高压设备投资大的问题，可望大大推进高压碳化反应在当前工业生产中的应用。（ 4 ）本发明工艺简单，便于控制，可实现碳化反应的连续化、规模化生产，产品质量优质、稳定，节能环保。如在生产高孔容二氧化硅中，通过调节参数，可方便获取高孔容二氧化硅、大比表面的微透明二氧化硅产品： BJH 孔容 >3.0 cm3/g，BJH 平均孔径 >20nm ， BET 比表面积 >600 cm2/g，其透明度、孔容、比表面积等性能均优于目前行业中的高档产品。
附图说明
图 1 为本发明所述加压碳化反应的装置的实施例 结构示意图。
具体实施方式
参见图 1 ，本发明实施例所述加压碳化反应的装置，包括雾化气罐 E-0 、复数压缩机、复数缓冲罐、复数预热器、加压液体罐 E-3 、喷嘴 N-1 、原料罐 E-5 、二氧化碳罐 E-6 、高压反应釜 E-9 、粗产品罐 E-10 、原料泵 P-3 、复数压力显示表、复数温度控制和显示表、复数背压阀和复数止回阀。
雾化器罐 E-0 出口接第一压缩机 P-1 入口和第一背压阀 V-1 回口，第一背压阀 V-1 入口与第一压缩机 P-1 出口相连，并经第一止回阀 V-2 接第一缓冲罐 E-1 入口，第一缓冲罐 E-1 出口经第二止回阀 V-3 接第一预热器 E-2 入口，第一预热器 E-2 出口接加压液体罐 E-3 第一入口。
原料罐 E-5 出口接原料泵 P-3 入口，原料泵 P-3 出口接第二预热器 E-4 入口，第二预热器 E-4 出口接加压液体罐 E-3 第二入口，加压液体罐 E-3 出口经第二止回阀 V-4 接喷嘴 N-1 入口，喷嘴 N-1 出口接高压反应釜 E-9 第一入口。
二氧化碳罐 E-6 出口接第二压缩机 P-2 入口和第二背压阀 V-5 回口，第二背压阀 V-5 入口与第二压缩机 P-2 出口相连，并经第三止回阀 V-6 接第二缓冲罐 E-7 入口，第二缓冲罐 E-7 出口经第四止回阀 V-7 接第三预热器 E-8 入口，第三预热器 E-8 出口接高压反应釜 E-9 第二入口。
高压反应釜 E-9 出口经第五止回阀 V-8 接粗产品罐 E-10 入口。第一缓冲罐 E-1 和第二缓冲罐 E-7 分别设压力显示表 P1 和 P2 ；加压液体罐 E-3 和高压反应釜 E-9 分别设温度控制和显示表 T1 和 T2 。
所述 的加压碳化反应的方法，采用所述加压碳化反应的装置，包括以下步骤：
1 ）称取一定量的固体物料溶解在溶剂（如：水等）中，或可适当加热至固体物料全部溶解在溶剂中。液体物料可根据反应需要调配至浓度为 0.1~4.0mol/L 左右。
2 ）开启设备，在 高压反应釜 E-9 中通入一定压力的二氧化碳，控制 高压反应釜 E-9 与 加压液体罐 E-3 的温度。然后再用 原料泵 P-3 将液体物料泵入 加压液体罐 E-3 中，使 加压液体罐 E-3 具有一定压力，并保证 加压液体罐 E-3 与 高压反应釜 E-9 有一定的压差。
3 ）待 高压反应釜 E-9 与 加压液体罐 E-3 中的温度、压力稳定后，开启第二止回阀 V-4 。保证 高压反应釜 E-9 与 加压液体罐 E-3 在稳定的压差下，液体物料经喷嘴 N-1 雾化后与 高压反应釜 E-9 中的二氧化碳气氛充分接触，快速反应。
4 ）保证 高压反应釜 E-9 中的液体物料在一定的液位时，打开第五止回阀 V-8 ，持续出料，得到反应产物。
步骤 1 ）中，所述液体物料指含有反应物的溶液、悬浮液，其中可以根据产品的需要加入添加剂。
步骤 2 ）中， 高压反应釜 E-9 与 加压液体罐 E-3 温度可设定在 10~100℃ 左右。
步骤 2 ）中， 高压反应釜 E-9 压力可控制在 0.1~15.0MPa ， 加压液体罐 E-3 压力可控制在 2.0~20.0MPa ，同时要保证 高压反应釜 E-9 的压力低于 加压液体罐 E-3 的压力。
步骤 2 ）中，保证 加压液体罐 E-3 与 高压反应釜 E-9 有一定的压差。其中 加压液体罐 E-3 中的压力可用 原料泵 P-3 通过泵入原料液实现，也可通过 第一压缩机 P-1 泵入高压惰性气体（如：氮气等）来达到所需压力。 高压反应釜 E-9 的压力可通过第二压缩机 P-2 泵入二氧化碳达到所需压力。
步骤 3 ）中，所述喷嘴可市购，且型号大小可根据设备的规模进行适当选型。或者雾化原料液也可以通过雾化气体对液体物料进行雾化实现。如通过第一压缩机 P-1 泵入高压惰性气体氮气控制 加压液体罐 E-3 压力为 10.0MPa ，第二压缩机 P-2 泵入二氧化碳控制 高压反应釜 E-9 压力为 4.0MPa ，这样也可将液体物料很好地雾化到 高压反应釜 E-9 中。
步骤 4 ）中反应产物的稳定排出可以通过控制第五止回阀来控制 高压反应釜 E-9 中的液位高度，从而实现连续排出。也可以累计到一定的液位高度后，再间歇排出。液位高度可以根据需要确定。
下面给出采用本实施例所述加压碳化反应的装置制备二氧化硅方法的实施例：
实施例 1
药品：九水合硅酸钠（国药集团化学试剂有限公司，分析纯），二氧化碳（厦门林德气体，纯度 ≥ 99.0% ）。
预备工作：自配 5L 0.25 mol/L 的硅酸钠溶液 ，预热温度控制在 25℃ 。高压反应釜中注入二样化碳，并用二氧化碳泵或压缩机和调压设备 ( 如背压阀系统 ) 将其稳定在 4.0MPa ，温度控制在 25℃ 。
第一步 保持加压液体罐压力为 8.0MPa ，温度控制在 25℃ ，通过喷嘴（ 500μm 孔）雾化硅酸钠溶液，把硅酸钠溶液雾化进入高压反应釜中。
第二步 从高压反应釜连续放料（放料速度约 1.49L /min ）。
后期处理：反应后的液体物料取少量用滴酸法测定碳酸氢钠的含量，计算硅酸钠的转化率为 99.5% 。反应后的液体物料洗涤（无碳酸氢根离子）、超临界干燥得到产品二氧化硅，用 ASAP2020 分析产品二氧化硅材料的性能，得其 BET 比表面积为 824m2/g ， BJH 孔容 4.53 cm3/g ， BJH 孔径 21.9nm 。用欧美克激光粒度分析仪分析产品二氧化硅材料的性能，得其粒径 D50 为 17.8μm 。
实施例 2
药品：九水合硅酸钠（国药集团化学试剂有限公司，分析纯），二氧化碳（厦门林德气体，纯度 ≥ 99.0% ）。
本实施例 2 与实施例 1 类似，区别在于： 保持原料罐压力为 12.0MPa 通过喷嘴（ 180μm 孔）雾化硅酸钠溶液，把硅酸钠溶液雾化进入高压反应釜中。
分析知硅酸钠的转化率为 99.7 % ，产品二氧化硅材料的 BET 比表面积为 710 m2/g ， BJH 孔容 4.55 cm 3/g ， BJH 孔径 27.7nm 。
实施例 3
药品：九水合硅酸钠（国药集团化学试剂有限公司，分析纯），二氧化碳（厦门林德气体，纯度 ≥ 99.0% ）。
本实例采用和实施例 1 一样的步骤，不同的是 : 第一步中保持原料釜压力为 10.0 MPa 通过喷嘴（ 500μm 孔）雾化硅酸钠溶液，把硅酸钠溶液雾化进入高压反应釜中。
分析知硅酸钠的转化率为 99.6% ，产品二氧化硅材料的 BET 比表面积为 732 m2/g ， BJH 孔容 5.11 cm 3/g ， BJH 孔径 28.9nm 。
实施例 4
药品：九水合硅酸钠（国药集团化学试剂有限公司，分析纯），二氧化碳（厦门林德气体，纯度 ≥ 99.0% ）。
本实例采用和实施例 1 一样的步骤，不同的是 : 配备 5L 0.75 mol/L 的硅酸钠溶液。
分析知硅酸钠的转化率为 99.4 % ，产品二氧化硅材料的 BET 比表面积为 677 m2/g ， BJH 孔容 5.18 cm 3/g ， BJH 孔径 28.6nm ，粒径 D50 为 20.2μm 。
实施例 5
药品：九水合硅酸钠（国药集团化学试剂有限公司，分析纯），二氧化碳（厦门林德气体，纯度 ≥ 99.0% ）。
本实例采用和实施例 1 一样的步骤，不同的是 : 第一步中保持原料釜压力为 12.0 MPa 通过喷嘴（ 500μm 孔）雾化硅酸钠溶液
分析知硅酸钠的转化率为 99.3 % ，产品二氧化硅材料的 BET 比表面积为 694m2/g ， BJH 孔容 4.52 cm 3/g ， BJH 孔径 25.9nm 。
实施例 6
药品：九水合硅酸钠（国药集团化学试剂有限公司，分析纯），二氧化碳（厦门林德气体，纯度 ≥ 99.0% ），正丁醇（国药集团化学试剂有限公司，分析纯）。
本实例采用和实施例 1 一样的步骤，不同的是 : 自配 5L 0.25 mol/L 的硅酸钠溶液，并加入添加剂正丁醇。
分析知硅酸钠的转化率为 100 % ，产品二氧化硅材料的 BET 比表面积为 820 m2/g ， BJH 孔容 4.53 cm 3/g ， BJH 孔径 18.6nm 。
实施例 7
药品：九水合硅酸钠（国药集团化学试剂有限公司，分析纯），二氧化碳（厦门林德气体，纯度 ≥ 99.0% ）， N,N- 二甲基甲酰胺（国药集团化学试剂有限公司，分析纯）。
本实例采用和实施例 1 一样的步骤，不同的是 : 自配 5L 0.25 mol/L 的硅酸钠溶液，并加入添加剂 N,N- 二甲基甲酰胺。
分析知硅酸钠的转化率为 99.2 % ，产品二氧化硅材料的 BET 比表面积为 848 m2/g ， BJH 孔容 5.38 cm3/g ， BJH 孔径 22.2nm ，粒径 D50 为 15.3μm 。
实施例 8
药品：偏铝酸钠（国药集团化学试剂有限公司，分析纯），二氧化碳（厦门林德气体，纯度 ≥ 99.0% ）。
本实例采用和实施例 1 一样的步骤，不同的是: 反应原料为液体偏铝酸钠溶液，煅烧产品为 γ-Al2O3 。
分析知偏铝酸钠的转化率为 77.4% ， 500℃ 煅烧
Figure 264
-三氧化二铝产品 BET 比表面积为 89.3 m2/g ， BJH 孔容为 0.41cm3/g ， BJH 孔径 24.8 nm 。
由实施例可见，采用所述加压碳化反应的装置和方法可实现高压下的快速碳化反应，实现连续的反应（指进出料连续）。而且转化率高，产品质量好。

Claims (8)

  1. 一种加压碳化反应的装置，其特征在于，包括雾化气罐、复数压缩机、复数缓冲罐、复数预热器、加压液体罐、喷嘴、原料罐、二氧化碳罐、高压反应釜、粗产品罐、原料泵、压力显示表、温度控制和显示表和复数背压阀；
    雾化器罐出口接第一压缩机入口和第一背压阀回口，第一背压阀入口与第一压缩机出口相连，并经第一止回阀接第一缓冲罐入口，第一缓冲罐出口经第二止回阀接第一预热器入口，第一预热器出口接加压液体罐第一入口；
    原料罐出口接原料泵入口，原料泵出口接第二预热器入口，第二预热器出口接加压液体罐第二入口，加压液体罐出口经第二止回阀接喷嘴入口，喷嘴出口接高压反应釜第一入口；
    二氧化碳罐出口接第二压缩机入口和第二背压阀回口，第二背压阀入口与第二压缩机出口相连，并经第三止回阀接第二缓冲罐入口，第二缓冲罐出口经第四止回阀接第三预热器入口，第三预热器出口接高压反应釜第二入口；
    高压反应釜出口经第五止回阀接粗产品罐入口；第一缓冲罐和第二缓冲罐均设压力显示表；加压液体罐和高压反应釜均设温度控制和显示表。
  2. 如权利要求1所述一种加压碳化反应的装置，其特征在于，高压反应釜第一入口设于其顶部或顶侧部。
  3. 一种加压碳化反应的方法，其特征在于，采用如权利要求1所述加压碳化反应的装置，包括以下步骤：
    1）称取固体物料并完全溶解在溶剂中，得到液体物料，液体物料储存于原料罐内，液体物料调配至浓度为0.1~4.0mol/L；
    2）开启设备，二氧化碳罐中的气体经第二压缩机通入高压反应釜中，控制高压反应釜和加压液体罐的温度，然后再用原料泵将液体物料泵入加压液体罐中，使加压液体罐具有压力，并保证加压液体罐与高压反应釜有压差；
    3）待高压反应釜与加压液体罐中的温度、压力稳定后，开启第二止回阀，保证高压反应釜与加压液体罐在稳定的压差下，液体物料经喷嘴雾化后与高压反应釜中的二氧化碳气氛充分接触，快速反应；
    4）保证高压反应釜中的液体物料在相应液位时，打开第五止回阀，持续出料，得到反应产物。
  4. 如权利要求3所述一种加压碳化反应的方法，其特征在于，步骤2）中，高压反应釜和加压液体罐温度为10℃~100℃。
  5. 如权利要求3所述一种加压碳化反应的方法，其特征在于，步骤2）中，高压反应釜压力为0.1~15.0MPa，加压液体罐压力为2.0~20.0MPa，高压反应釜的压力低于加压液体罐的压力。
  6. 如权利要求3所述一种加压碳化反应的方法，其特征在于，步骤2）中，加压液体罐中的压力通过泵入液体物料实现，或通过第一压缩机泵入高压惰性气体来达到所需压力；高压反应釜的压力通过第二压缩机泵入二氧化碳达到所需压力。
  7. 如权利要求3所述一种加压碳化反应的方法，其特征在于，步骤3）中，通过第一压缩机泵入高压惰性气体控制加压液体罐压力为10.0MPa，通过第二压缩机泵入二氧化碳控制高压反应釜压力为4.0MPa。
  8. 如权利要求3所述一种加压碳化反应的方法，其特征在于，步骤4）中，通过第五止回阀控制高压反应釜中的液位高度，实现反应产物连续稳定排出。
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