CN219670196U - Hydrodeoxygenation polishing system - Google Patents
Hydrodeoxygenation polishing system Download PDFInfo
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- CN219670196U CN219670196U CN202320054403.9U CN202320054403U CN219670196U CN 219670196 U CN219670196 U CN 219670196U CN 202320054403 U CN202320054403 U CN 202320054403U CN 219670196 U CN219670196 U CN 219670196U
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- 239000001257 hydrogen Substances 0.000 claims abstract description 57
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Abstract
The utility model discloses a hydrodeoxygenation polishing system, which structurally comprises a first membrane contactor, a mixed flow controller, a photolysis reactor, a double-layer polishing tower and a second membrane contactor. Wherein, the first membrane contactor is internally provided with a hydrogen absorption membrane for preparing hydrogen-rich water. The double-layer polishing tower is of a laminated structure and comprises a containing part, a supply part and a discharge part, and the surface oxide layer of the metal nano particles is eliminated through the hydrogenation reaction of oxygen. The combined system of the first membrane contactor, the double-layer polishing tower and the second membrane contactor can remove oxygen in a better depth manner, so that the degradation reaction efficiency of the free radical composite oxidant is improved, and the conversion rate of hydrogen is obviously improved.
Description
Technical Field
The utility model relates to a method and a device for removing oxygen and a free radical composite oxidant in a pure water manufacturing process, in particular to a finishing polishing system with a hydrodeoxygenation function.
Background
In the production and manufacture of very large scale integrated circuits, the growth rate of native oxide on the silicon surface needs to be tightly controlled. Layer-by-layer growth of native oxide can occur on the surface of silicon in air, while native oxide growth on a silicon wafer in ultrapure water reduces the atomic density at the oxide-silicon interface as silicon dissolves into water, creating a rough native oxide film surface. The natural oxide film formed on the surface prevents low-temperature growth of high-quality epitaxial silicon films, prevents accurate control of thickness and electrical properties of extremely thin gate oxide films, and increases contact resistance of small-area through holes. Thus, as integrated circuit feature sizes decrease, the formation and growth of native oxide films is receiving increasing attention.
Oxygen and water or moisture co-action is required to grow an oxide film on a clean silicon wafer. By reducing the water concentration in the air and the dissolved oxygen concentration in the ultrapure water, the growth rate of the oxide film in the air and the ultrapure water can be effectively reduced.
In addition to affecting the growth of native gate oxide, dissolved oxygen in ultrapure water also enhances corrosion of metals such as copper at higher concentrations. Although the semiconductor material standard specifies ultra pure water POD end dissolved oxygen of 10ppb or less for high-end processes, very critical processes (e.g., siGe equipment cleaning) may require lower control values, such as requiring dissolved oxygen of 1ppb or less. This, of course, needs to be accomplished when the tank is closed to the environment.
In the prior process ultrapure water preparation process, the finishing polishing system usually adopts a membrane degassing mode to realize the desorption of dissolved gas so as to achieve the purpose of removing oxygen and other dissolved gases. Due to the application of AOPs technology and photocatalytic oxidation technology, an oxidant (free radical composite oxidant) formed by compositing free radicals generated by a photolysis reactor in a polishing process can also enhance the process corrosion of metals such as copper, and in the back-end of the semiconductor process, the pore corrosion of the lower concentration secondary oxidant on the surface of a wafer has been found by SPM (scanning probe microscope).
The research shows that the metal nanoparticle catalyst assembled by noble metal nano colloid particles and ion exchange resin can quench the secondary oxidant effectively, but dissolved oxygen in water can easily form an oxide layer on the surface of the metal particles to damage the structure of the high molecular catalyst, so that the nano particles fall off, the activity of the catalyst is obviously reduced, and the service life of the catalyst is shortened. How to further deeply remove the dissolved oxygen in the water by using the heterogeneous nano catalytic technology and effectively avoid the damage of oxide to the matrix of the catalyst so as to prolong the service life of the catalyst, thereby constructing a novel finishing polishing treatment system, and becoming the key of the research of the technicians in the field.
Accordingly, based on the above-described technical problems, there is a need for developing a hydrodeoxygenation polishing system.
Disclosure of Invention
The utility model aims to provide a hydrodeoxygenation polishing system which is mainly suitable for manufacturing new energy batteries, novel semiconductor displays, third-generation semiconductor materials and devices, is particularly suitable for a preparation system of ultrapure water for advanced process cleaning in high-end chip production, can obviously improve the conversion rate of hydrodeoxygenation of a secondary oxidant of the polishing system, improves the removal efficiency of dissolved oxygen, obtains higher catalyst reaction rate and more stable and excellent ion polishing effect by utilizing a double-layer polishing tower, and effectively solves the technical problem of new preparation of cleaning water with shortened service life due to oxidation of the surface of a catalyst or pollution of acidic oxidation substances.
In order to achieve the above object, the present utility model provides the following technical solutions:
the utility model provides a hydrodeoxygenation polishing system, comprising:
a double-layer polishing tower;
a photolysis reactor positioned at the process upstream end of the double-layer polishing tower;
the first membrane contactor is positioned at the process upstream end of the double-layer polishing tower and is arranged in parallel with the photolysis reactor, a hydrogen absorption membrane is arranged in the first membrane contactor, and the first membrane contactor is provided with a high-purity hydrogen supply system; and
a second membrane contactor is arranged at the downstream of the double-layer polishing tower;
the double-layer polishing tower is sequentially divided into a supply part, a containing part and a discharge part along the process flow;
the supply part of the double-layer polishing tower receives the to-be-extracted water supplied from the upstream of the process and supplies the to-be-extracted water to the accommodating part;
the accommodating part is divided into two layers of areas along the process flow, namely a hydrogenation reaction area near one side of the supply part and an ion exchange area near one side of the discharge part;
the accommodating part sequentially processes the purified water to be purified through the hydrogenation reaction area and the ion exchange area to obtain purified water, and the accommodating part conveys the purified water to the discharge part and discharges the purified water to the downstream end of the process through the discharge part.
In the system of the utility model, the first membrane contactor is internally provided with a hydrogen absorption membrane, is arranged at the front stage of the double-layer polishing tower, and enables water to be purified to absorb high-purity hydrogen by a hydrogen purging mode, and is preferably connected into the polishing system by adopting a mixed flow ratio adjusting mode to be mixed with the effluent water of the photolysis reactor; setting a mixed flow controller at the rear stage of the first membrane contactor, and controlling the preparation amount of the hydrogen-rich water through the concentration proportion of dissolved hydrogen in the mixed liquid phase; the double-layer polishing tower is arranged at the rear stage of the photolysis reactor, and the mixed water to be purified enters the double-layer polishing tower; the double-layer polishing tower completes the rapid quenching of the free radical composite oxidant and the polishing adsorption of all ions, and the effluent water enters a second membrane contactor; and the second membrane contactor carries out gas stripping and desorption on various dissolved gases in water to be purified in a nitrogen purging mode, and then tiny particles including bacteria are removed through a micro-particle membrane separator to form purified water.
In addition, the hydrogenation reaction area of the double-layer polishing tower is filled with a supported metal nanoparticle catalyst, and the ion exchange area is filled with a mixed ion exchange resin; the supported metal nanoparticle catalyst can decompose and reduce the free radical composite oxidant generated by the photolysis reactor to generate by-product oxygen, the oxygen and the first membrane contactor absorb hydrogen entering the water phase, and the hydrogen is activated into adsorbed hydrogen atoms and adsorbed atomic oxygen by the higher dissociation energy of the catalyst, so that the selective heterogeneous catalytic hydrogenation reaction is carried out on the surface of the catalyst to reduce the hydrogen into water.
The concentration of dissolved hydrogen in the hydrogen-rich water prepared by the first membrane contactor is controlled to be 0.05-0.1 mg/l, and the mixed flow ratio of the hydrogen-rich water prepared by the first membrane contactor is 3% -10%.
From the economical cost of practical operation, the hydrogen-rich water is formed by the mixed flow of hydrogen which is more than theoretical equivalent and the selective hydrogenation reaction of heterogeneous catalysis with oxygen, so that the dissolved oxygen in the water is reduced at lower cost, and the surface oxidation of the nano metal catalyst is dynamically avoided, thereby prolonging the service life.
Further, the downstream end of the second membrane contactor is connected with a microparticle membrane separator;
the second membrane contactor is provided with a high purity nitrogen gas supply system.
Further, the accommodating part of the double-layer polishing tower can be divided into a double-chamber structure comprising the hydrogenation reaction area and the ion exchange area through an orifice plate.
Further, the double-layer polishing tower is provided with two sub-accommodating parts connected in series according to the process flow, and the sub-accommodating parts are sequentially configured into a hydrogenation reaction area and an ion exchange area according to the process flow.
The supported metal nanoparticle catalyst comprises noble metals in VIII family metals or colloid particles of transition group noble metals in IB family metals, and is supported on a carrier. Compared with a single metal nanoparticle catalyst, the alloy composite nanoparticle catalyst represented by the binary metal nanoparticle catalyst can decompose and quench a secondary oxidant (free radical composite oxidant) in the pure water to be extracted more rapidly and efficiently, deeply removes oxygen, and does not pollute the water quality in an ultrapure liquid phase environment.
Further, the particle size of the colloidal particles of the supported metal nanoparticle catalyst is 1 nm-30 nm;
the size of the metal nanoparticles and the associated average surface coordination can affect the binding energy of the reaction intermediates at the surface of the metal catalyst, which in turn affects the reduction rate of the hydrogenation and decomposition reactions. In the particle size range of 1-30 nm, the metal nano particles can be extremely rapidly decomposed and quenched to the secondary oxidant in the water to be extracted, and have higher selectivity.
The contact time of the supported metal nanoparticle catalyst and the water to be purified containing hydrogen peroxide is 2 s-45 s, namely, the space velocity SV=80 h -1 ～1800h -1 。
Further, the resistivity of water to be purified entering the photolysis reactor is not less than 17MΩ. cm, TOC concentration is not more than 10 μg/l, and the water is deep desalted water after deep desalting. By controlling the water inlet condition of the polishing system, photochemically active anions in inorganic salt and micro-pollutants in water to be purified compete together to absorb photons, so that adverse effects of degradation efficiency of a photolysis reactor are suppressed to the minimum extent, and the method becomes an important precondition for efficient purification of water in the hydrodeoxygenation polishing system.
In the technical scheme, the hydrodeoxygenation polishing system provided by the utility model has the following beneficial effects:
the system of the utility model can effectively improve the reduction efficiency of dissolved oxygen in the polishing system, remarkably improve the conversion rate of decomposition and hydrogenation of the free radical composite oxidant, not only degrade and reduce the secondary oxidant to a concentration below 1 mug/l, but also fundamentally solve the key technical problem that the service life of the catalyst is shortened due to the pollution of dissolved oxygen and weak acidic oxidation substances, and prolong the service life of the catalyst with lower cost guarantee, so that the catalyst can be recycled effectively and permanently, thereby having important practical application value and industrial popularization significance.
Drawings
In order to more clearly illustrate the embodiments of the present utility model or the technical solutions in the prior art, the drawings required for the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments described in the present utility model, and other drawings may be obtained according to these drawings for a person having ordinary skill in the art.
FIG. 1 is a process flow diagram of a hydrodeoxygenation polishing system according to an embodiment of the utility model;
FIG. 2 is a schematic view of a double-layer polishing tower of a hydrodeoxygenation polishing system according to an embodiment of the utility model;
FIG. 3 is a schematic diagram of a hydrogen rich water production system for a hydrodeoxygenation polishing system according to an embodiment of the utility model;
FIG. 4 shows four catalyst hydrogenation reactions H of a hydrodeoxygenation polishing system according to an embodiment of the utility model 2 Graph of addition amount and residual DO amount (mixed flow ratio 5%);
FIG. 5 shows four catalyst hydrogenation reactions H of a hydrodeoxygenation polishing system according to an embodiment of the utility model 2 Graph of the amount added versus residual DO level (mixed flow ratio 8%).
Reference numerals and abbreviations description:
1. pure water tank (di.tank); 2. a photolytic reactor (TOC-UV); 3. mixed flow controller (Actival CV); 4. a first membrane contactor (DHMC); 5. high heightPure Hydrogen (PH) 2 Gas); 6. a double-layer polishing tower; 7. a second membrane contactor (DOMC); 8. high Purity Nitrogen (PN) 2 Gas); 9. a particulate membrane separator (PMS-UF);
601. a supply unit; 602. a discharge section; 603. a housing part;
60301. supported metal nanoparticle catalysts (cavity. Bed);
60302. mixed ion exchange resin (MB-P).
Detailed Description
In order to make the technical scheme of the present utility model better understood by those skilled in the art, the present utility model will be further described in detail with reference to the accompanying drawings.
See fig. 1-5;
a hydrodeoxygenation polishing system of the present embodiment, the system comprising:
a double-layer polishing tower 6;
a photolysis reactor 2 positioned at the process upstream end of the double-layer polishing tower 6;
the first membrane contactor 4 is positioned at the process upstream end of the double-layer polishing tower 6 and is arranged in parallel with the photolysis reactor 2, a hydrogen absorption membrane is arranged in the first membrane contactor 4, and the first membrane contactor 4 is provided with a high-purity hydrogen supply system; and
a second membrane contactor 7 is arranged at the downstream of the double-layer polishing tower 6;
the double-layer polishing tower 6 is divided into a supply part 601, a containing part 603 and a discharge part 602 in sequence along the process flow;
the supply part 601 of the double-layer polishing tower 6 receives water to be purified supplied upstream of the process and supplies water to be purified to the housing part 603;
the housing portion 603 is divided into two regions along the process flow, namely a hydrogenation reaction region near the supply portion 601 and an ion exchange region near the discharge portion 602;
the housing portion 603 sequentially processes the water to be purified through the hydrogenation reaction zone and the ion exchange zone to obtain purified water, and the housing portion 603 conveys the purified water to the discharge portion 602 and discharges the purified water to the downstream end of the process through the discharge portion 602. The water to be treated is decomposed and removed by the supported metal nanoparticle catalyst 60301, and then is subjected to ion exchange treatment after being quenched by the mixed ion resin 60302. The process can not only prevent the mixed ion resin 60302 from degradation and decomposition by the secondary oxidant, ensure higher exchange efficiency of the resin and prolong the service life of the resin, but also effectively remove dissolved oxygen in water and the dissolved oxygen increased by the decomposition of the oxidant through the catalyst.
In the housing portion, by disposing the supply portion 601 on the upper side and disposing the discharge portion 602 on the lower side thereof, and supplying the water to be purified from the supply portion 601 in a flow manner from top to bottom, the two layers of filler are less likely to be stirred and disturbed by the water to be purified, and the supported metal nanoparticle catalyst 60301 and the mixed ion exchange resin 60302 are kept in a two-layer structure.
Preferably, the housing portion 603 of the double-layer polishing tower 6 may be divided into a double-chamber structure including a hydrogenation reaction area filled with the supported metal nanoparticle catalyst 60301 and an ion exchange area filled with the mixed ion exchange resin 60302 by an orifice plate (not shown). In a preferred embodiment, the housing is internally provided with an orifice plate for separation, a water distribution device and a connecting mechanism. Through the arrangement, a double-chamber bed structure can be formed, the mixing of two fillers can be effectively prevented, and further, the process sequence of the water to be treated, which is subjected to the separation and quenching of the free radical composite oxidant by the supported metal nanoparticle catalyst 60301 and then the fine treatment and polishing by the mixed ion exchange resin 60302, is ensured.
As an extended implementation manner, the accommodating portion 603 of this embodiment is provided with two sub-accommodating portions connected in series according to a process flow, and the sub-accommodating portions are sequentially configured into a hydrogenation reaction area and an ion exchange area according to the process flow. Further, the sub-housing portion configured as the hydrogenation reaction region may be a separate cylindrical structure or a tubular cylindrical cavity structure. The manner in which the lamination process of the double-layer structure can be achieved is various, and will not be described in detail here.
In the double-layer polishing tower, the supported metal nanoparticle catalyst 60301 filled in the housing portion 603 includes a supported single metal nanoparticle catalyst and a binary metal composite nanoparticle catalyst or a multi-alloy composite nanoparticle catalyst. The supported metal nanoparticle catalyst 60301 is preferably a noble metal of group viii or a colloidal particle of a transition group noble metal of group IB, and is supported on a carrier. Examples of the noble metal in group VIII include platinum, palladium, iridium, rhodium, osmium and ruthenium, examples of the noble metal in group IB include gold and silver, and these metal nanoparticles may be used singly or in combination of two or more kinds, or may be used by alloying two or more kinds.
In order to increase the catalyst activity (utilization ratio of metal atoms) and to save the amount of noble metal used, these metal nanoparticles may be dispersed and immobilized on an inorganic support or an organic support in a specific manner. Examples of the carrier supporting the metal nanoparticles include alumina, silica-alumina, titania, zirconia, ceria, activated carbon, and functional resins typified by ion exchange resins. Further preferably, the metal nanoparticle catalyst is obtained by dispersing metal nanoparticles on an anion exchange resin and supporting the dispersed metal nanoparticles. Particularly preferred are binary metal composite nanoparticle catalysts composed of two noble metals of group VIII and group IB or independent group VIII alloyed by using quaternary ammonium group macroporous or gel type anion exchange resins with hydroxyl functional groups as functional carriers, such as palladium gold nanoparticle catalysts or palladium platinum nanoparticle catalysts.
It has been found that under the preferred weakly alkaline conditions, the electron donor on the surface of the metal nanoparticle can be converted into OH - Three oxygen free radicals are generated through branching and transfer of chains to drive the kinetic process of the chain reaction together, so that the water phase H 2 O 2 Accelerating consumption and decomposition while generating oxygen, the thermochemical equation is expressed as:
H 2 O 2 (l)＝H 2 O(l)+1/2O 2 (g)ΔH＝-105.8kJ.mol -1
compared with single metal colloid particles, the binary metal composite nano particles have the advantages that the active components are highly dispersed due to the introduction of the second metal atoms, and the two metals form a synergistic effect in the catalytic reaction, so that the binary metal composite nano particles can show ultrahigh catalytic activity, and further have better catalytic rate, reaction activity, selectivity and stability.
A specific study showed Pd 0 Easier H-conversion 2 O 2 The catalyst is adsorbed on the surface of Pd-Au bimetallic alloy catalyst, and experiments further prove that the coordination effect, the dilution effect and the electronic effect exist between Pd and Au. The introduction of Au causes the active component to be highly dispersed, the Au gathers to the surface, dilutes the Pd on the surface, increases the number of isolated Pd sites, and the charge transfer from Pd to Au leads to the increase of the content of PdO, while Pd 0 PdO is critical to achieving optimal catalytic performance. Since the introduction of Au can increase the Pd position of the monomer and reduce the Pd position of the connector, the former is more beneficial to H in alkaline environment 2 O 2 The main active site of decomposition increases the selectivity of the decomposition reaction in the hydrogen-oxygen kinetic synthesis reaction.
For binary metal composite nano particles or single metal colloid particles, hydrogen peroxide can be rapidly decomposed, so that the hydrogen peroxide is relatively insoluble in a supported anion exchange resin, and TOC (total organic carbon) is dissolved out of the resin or the resin is deteriorated. The binary metal composite nano particles have higher catalytic rate, so that the functionalized PS carrier has an excellent effect of more effectively controlling the dissolution of organic impurities.
Preferably, the contact time between the supported metal nanoparticle catalyst 60301 and the water to be purified containing hydrogen peroxide of the embodiment is 2 s-45 s, i.e. space velocity sv=80 h -1 ～1800h -1 . More preferably space velocity sv=300 h -1 ～1500h -1 The decomposition efficiency of the free radical composite oxidant is not lower than 98%.
The method for preparing the supported metal nanoparticles is not particularly limited, and examples thereof include a coprecipitation method, an immersion method, a precipitation deposition method, a colloid precipitation method, a gas phase grafting method, a solid phase grinding method, and the like, and the preparation process of the binary metal nanoparticles is complicated compared with the preparation of the single metal nanoparticles, and the alloy nanoparticles which are relatively uniformly mixed can be obtained by adjusting and optimizing synthesis parameters. At present, the preparation method of the binary metal nano particles mainly comprises the following steps: deposition precipitation, impregnation, colloid, etc. Among these methods, the colloid method is more useful for obtaining alloy particles having uniform composition, particle size and shape, and further can significantly improve the catalytic performance after loading. According to a colloid method for experiments, for example, precursor solution of noble metal of group VIII is dissolved in tetrahydrofuran, an equimolar amount of phenethyl mercaptan is added, stirring is continued, then triethylamine metal complex (adjustable proportion of bimetallic component) which is synthesized by reducing noble metal of group IB by diphenyl sulfide is added, stirring is continued, then sodium borohydride solution is rapidly poured, stirring is continued, reactive solvent is removed by rotary evaporation at room temperature, the remaining sample contains water and oil phases, the oil phase is washed three times with methanol to remove residual reducing agent and phenethyl mercaptan, and then dichloromethane is used for extraction, so that binary metal nano particles can be prepared.
In the double-layer polishing column 6, the mixed ion exchanger charged in the housing portion 603 is preferably two kinds of ion exchange resins each having an alkali group and an acid group, which are preliminarily mixed, and more preferably a high-purity-grade mixed ion exchange resin having a elution concentration ΔTOC of 1. Mu.g/l or less and being non-renewable is used. The water to be treated is decomposed and removed by the supported metal nanoparticle catalyst 60301 from top to bottom, and then dissolved pollutants such as trace metal ions, nonmetallic ions, weakly ionized inorganic salts, residual organic impurities and the like in the water are deeply removed and absorbed by the mixed ion exchange resin 60302. Compared with the traditional process, the double-layer polishing tower 6 can prevent the high-purity grade mixed ion exchange resin 60302 from being degraded by the secondary oxidant, ensure higher exchange efficiency of the exchanger and prolong the service life of the exchanger.
In the heterogeneous catalytic reaction on the surface of the nano metal particle catalyst, a small amount of hydrogen generated by deprotonation reaction of hydration hydrogen ions in the photolysis reactor will react with the catalytic by-product oxygen to generate water.
In a typical finishing polishing system, hydrogen tends to be substantially less than the equivalent concentration of hydrogen peroxide due to the fact that the system is also affected by the membrane degasser in the upstream process section (secondary desalting section), so that the surface of the nano-metal particle catalyst accumulates oxygen and is exposed to an oxidizing environment for a long period of time, thereby forming an oxide layer which can be reduced in the initial stage of surface oxidation; the oxygen accumulation also causes the degradation and disconnection of the skeleton of the high molecular polymer of the catalyst carrier, and in addition, the organic acid load generated in the process of the photolysis reactor 3 may exceed the concentration value calculated predictably, and the TOC effect from the relatively high concentration at the upstream is generated, so that the problems of surface oxidation, performance reduction, conversion rate reduction, colloid particle shedding, service life shortening and the like of the nano metal particle catalyst are easy to occur after the nano metal particle catalyst is used for a period of time.
In order to effectively solve the problems, the utility model provides a solution for hydrodeoxygenation, which not only can fundamentally avoid the formation of a catalyst oxide film, but also plays a very effective auxiliary role in deep removal and control of dissolved oxygen.
In the parallel treatment section of the polishing system, hydrogen-rich water is prepared through the first membrane contactor 4, and in the supply part 601 of the double-layer polishing tower 6, the water to be purified and the hydrogen-rich water generate mixed flow effect to obtain hydrogen concentration larger than theoretical equivalent, and then the mixed water to be purified is subjected to dynamic flow, so that the nano metal catalyst under normal pressure can remove oxygen under an optimally selected reaction condition, and the dissolved oxygen in the water is effectively reduced.
It has been found that group VIII metals, such as Pd (outer electron arrangement 4d 10 5s 0 ) Under certain external conditions, d-orbit electrons can transit to s-orbit to form d-band holes, so that chemical adsorption is generated, and H is activated 2 And O 2 。H 2 After Pd catalyst activation, H-H bond is dissociated to form adsorbed hydrogen atom, O-O bond is not dissociated easily to form adsorbed molecular oxygen, and the adsorbed hydrogen atom and oxygen molecule synthesize transition state peroxy matter first. The dissociation energy of the O-O bond provided by Pd active site is an optimized reaction condition, under which O-O bond is broken to form adsorption atomic oxygen, then hydrogenation is carried out to generate adsorption hydroxyl, and then the recombination reaction is carried out to generate H 2 O. Thermochemical equation tableThe method is shown as follows:
H 2 (g)+1/2O 2 (g)＝H 2 O(l)ΔH＝-241.6kJ.mol- 1
further studies have found that for palladium-based metal nanoparticle catalysts, the addition of hydrogen will also be more conducive to hydrogenation reactions that directly occur to reductively decompose the free radical complex oxidant.
Further studies have found that the size of the metal nanoparticles and the associated average surface coordination affect the binding energy of the nano-metal catalyst surface reaction intermediate and thus H 2 The rate of O formation. Due to the catalyst surface O 2 The dissociation activation energy barrier is higher, the particle size of the metal nano particles will be opposite to H 2 The rate of O formation has an effect. In the present utility model, the average particle diameter of the metal nanoparticles is preferably 1 to 30nm, more preferably 1.2 to 20nm, and even more preferably 1.2 to 5 nm.
According to a chain reaction kinetic equation, after the dissociation products of the transition state peroxy substances undergo hydrogenation and a composite reaction, chain interruption occurs, and then hydrogen is generated by gas phase destruction. Residual hydrogen in the reaction and residual dissolved oxygen in water are stripped and desorbed by a postposition second membrane contactor 7 in a nitrogen blowing mode, so that the final desorption effect is achieved.
The electron acceptors participating in the selective hydrogenation reaction of the accommodating part comprise byproducts generated in the process of quenching the free radical composite oxidant, and also comprise trace dissolved oxygen in the water to be extracted, so that more dissolved oxygen in the water can be reduced and removed in the complex catalytic reaction by sufficient hydrogen.
In the supply portion 601 of the double-layer polishing tower 6, hydrogen-rich water having a mixed flow effect with water to be purified is produced by the first membrane contactor 4. The first membrane contactor 4 is internally provided with a membrane module, and the membrane module is converted into a hydrogen absorption membrane (hydrogen membrane for short) by changing a purging medium and adjusting vacuum pressure and reversely applying a degassing membrane principle, for example, the membrane module can be a hollow fiber membrane, so that the aim of filling hydrogen into ultrapure water is fulfilled.
In the first membrane contactor 4, the hydrogen concentration in the hydrogen-rich water can be controlled by adjusting the hydrogenation flow and the pressure, and the hydrogen dissolution concentration of the hydrogen-rich water is preferably controlled between 0.05 and 0.1 mg/l.
Preferably, the first membrane contactor 4 of the present embodiment is connected to the system by means of mixed flow ratio adjustment. The mixing flow ratio of the hydrogen-rich water is 3-10%, preferably 5-8%.
The mixed flow controller 3 is arranged at the rear stage of the first membrane contactor 4, and the preparation amount of the hydrogen-rich water is controlled and regulated through the concentration proportion of the dissolved hydrogen in the mixed liquid phase, and preferably, the crossover water amount of the hydrogen-rich water with 1-5% is reserved to be supplied to the second membrane contactor 7.
According to the system, the nano metal catalyst activates hydrogen with a higher dissociation energy into adsorbed hydrogen atoms and adsorbed atomic oxygen with the oxygen generated by decomposing the free radical composite oxidant in an amount larger than the theoretical equivalent, so that a selective heterogeneous catalytic hydrogenation reaction continuously occurs on the surface of the catalyst to generate water. The dynamic running system not only fundamentally solves the problems of surface oxidation, performance reduction and service life shortening of the catalyst after long-time use and avoids the reduction steps of limited recovery such as operation interruption, extraction, soaking, cleaning and the like and pollution risks, but also can reduce the dissolved oxygen in continuous running to a lower level, such as 0.1-0.5 mug/l under the condition that the obtained free radical composite oxidant is efficiently removed to less than 1 mug/l.
The second membrane contactor 7 is provided with a deoxidizing membrane, for example, a hollow fiber membrane, and is provided with a high-purity nitrogen gas supply system as a final degassing device to finally remove hydrogen gas which is not converted in the reaction and dissolved oxygen remained in water.
Preferably, the downstream end of the second membrane contactor 7 of this embodiment is connected to a fine particle membrane separator 9, which can remove fine particles including bacteria.
In addition, in order to ensure the better effect of degrading organic matters in the photolysis reactor 2, the adverse effect of the co-competition of photochemically active ions in inorganic salt and micro-pollutants in water to be purified for absorbing photons is reduced to the minimum, and the water to be purified entering the polishing system should comprise the following water quality characteristics: the resistivity is not less than 17MΩ.cm, the TOC concentration is not more than 10 μg/l, and the deep desalted water after deep desalting is obtained.
Examples (example)
Hydrogen rich water was prepared by fig. 3 and was fed into the implementation system according to fig. 1 at a 5% mixed flow ratio. Four kinds of nano particles are prepared by an in-situ reduction method and a heterogeneous agglomeration method, and the particle sizes of the HR-TEM image characterization colloid are respectively as follows: gold nanoparticles 1.9+ -0.3 nm, palladium nanoparticles 1.7+ -0.3 nm, palladium gold nanoparticles 2.0+ -0.4 nm and platinum nanoparticles 2.1+ -0.4 nm. Four kinds of supported nanoparticle catalysts are sequentially and individually filled into the accommodating part 603 of the double-layer polishing tower 6 near the side of the feeding part 601, and the dissolved oxygen concentration of the liquid phase outlet of the second membrane contactor 7 is detected when the concentration of hydrogen at the liquid phase outlet of the hydrogen absorption membrane is respectively 0.05mg/l, 0.06mg/l, 0.07mg/l, 0.08mg/l, 0.09mg/l and 0.1mg/l in four times of tests, and the results are plotted as shown in fig. 4.
The mixed flow ratio was changed to 8%, the above test was repeated, and the hydrogen addition amount of the hydrogen-rich water was also compared with the residual dissolved oxygen amount at the liquid phase outlet of the second membrane contactor as data, and a curve was drawn, see fig. 5.
The above test is directed to the application effect detection of the hydrodeoxygenation capabilities of the novel polishing system. As can be seen from FIGS. 4 and 5, the reaction rates K and H due to hydrodeoxygenation 2 Concentration, H 2 O 2 The product of the concentrations is proportional, and increasing the hydrogen concentration in the hydrogen-rich water will remove more dissolved oxygen. Thus, the system is operated to better achieve the expected effect of further deep deoxidization, and can remove dissolved oxygen to the Detection Limit (DL) level. The polishing system with hydrodeoxygenation capability can reduce the operation load and investment cost of a terminal membrane degasser, obtain lower micro-pollution index of controllable preparation, and play an important role in protecting the metal nanoparticle catalyst from surface oxidation and matrix degradation.
Finally, it should be noted that: the described embodiments are intended to be only a few, but not all, of the many other embodiments of the present utility model that a person of ordinary skill in the art would achieve without inventive effort based on the embodiments herein are within the scope of the present utility model.
In the technical scheme, the hydrodeoxygenation polishing system provided by the utility model has the following beneficial effects:
the system of the utility model can effectively improve the reduction efficiency of dissolved oxygen in the polishing system, remarkably improve the conversion rate of hydrodeoxygenation of the free radical composite oxidant, not only degrade and reduce the secondary oxidant to a concentration below 1 mug/l, but also fundamentally solve the key technical problem of shortening the service life of the catalyst due to pollution of dissolved oxygen and weak acidic oxidation substances, and prolong the service life of the catalyst with lower cost guarantee, so that the catalyst can be recycled efficiently and permanently, thereby having important practical application value and industrial popularization significance.
While certain exemplary embodiments of the present utility model have been described above by way of illustration only, it will be apparent to those of ordinary skill in the art that modifications may be made to the described embodiments in various different ways without departing from the spirit and scope of the utility model. Accordingly, the drawings and description are to be regarded as illustrative in nature and not as restrictive of the scope of the utility model, which is defined by the appended claims.
Claims (6)
1. A hydrodeoxygenation polishing system, the system comprising:
a double-layer polishing tower (6);
a photolysis reactor (2) positioned at the process upstream end of the double-layer polishing tower (6);
the first membrane contactor (4) is positioned at the process upstream end of the double-layer polishing tower (6) and is arranged in parallel with the photolysis reactor (2), a hydrogen absorption membrane is arranged in the first membrane contactor (4), and the first membrane contactor (4) is provided with a high-purity hydrogen supply system; and
a second membrane contactor (7) is arranged at the downstream of the double-layer polishing tower (6);
the double-layer polishing tower (6) is sequentially divided into a supply part (601), a containing part (603) and a discharge part (602) along the process flow;
a supply part (601) of the double-layer polishing tower (6) receives water to be purified supplied upstream of a process and supplies water to be purified to the accommodating part (603);
the accommodating part (603) is divided into two layers of areas along the process flow, namely a hydrogenation reaction area near the side of the supply part (601) and an ion exchange area near the side of the discharge part (602);
the accommodating part (603) sequentially processes the purified water to be purified through the hydrogenation reaction area and the ion exchange area to obtain purified water, and the accommodating part (603) conveys the purified water to the discharging part (602) and discharges the purified water to the downstream end of the process through the discharging part (602).
2. Hydrodeoxygenation polishing system according to claim 1, characterized in that the process downstream end of the first membrane contactor (4) is connected with a mixed flow controller (3) to access the system by means of mixed flow ratio regulation;
the concentration of dissolved hydrogen of the hydrogen-rich water prepared by the first membrane contactor (4) is controlled to be 0.05-0.1 mg/l, and the mixed flow ratio of the hydrogen-rich water prepared by the first membrane contactor (4) is 3% -10%.
3. Hydrodeoxygenation polishing system according to claim 1, characterized in that the process downstream end of the second membrane contactor (7) is connected to a fine particle membrane separator (9);
the second membrane contactor (7) is provided with a high purity nitrogen gas supply system.
4. Hydrodeoxygenation polishing system according to claim 1, wherein the housing (603) of the double-layer polishing tower (6) is dividable by an orifice plate into a double-chamber structure comprising the hydrogenation reaction zone and the ion exchange zone.
5. Hydrodeoxygenation polishing system according to claim 1, characterized in that the double-layered polishing tower (6) is provided with two sub-receptacles in series according to a process flow, which are configured as a hydrogenation reaction zone and an ion exchange zone in sequence according to a process flow.
6. Hydrodeoxygenation polishing system according to claim 1, characterized in that the water to be purified entering the photolysis reactor (2) has a resistivity not less than 17mΩ. cm, a TOC concentration not greater than 10 μg/l and is deep desalted water after deep desalting.
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