CN105050965A - pH control to enable homogeneous catalytic wet air oxidation - Google Patents

Abstract

A system and method for the treatment of process streams is provided. A catalyst mediates a wet oxidation process at elevated temperatures and pressures for treating at least one undesirable constituent in an aqueous mixture. A catalyst may be selected for its solubility at a detected pH level of the aqueous mixture. Alternatively, a pH level of the aqueous mixture may be adjusted to solubilize a selected catalyst and/or maintain the selected catalyst in a soluble form. A controller in communication with a pH sensor may be configured to generate a control signal to adjust the pH level of the aqueous mixture in response to the pH sensor registering a pH level outside a predetermined pH solubility range for a selected catalyst.

Description

The pH realizing homogeneous catalysis wet air oxidation controls

To the cross reference of related application

The application is the US application serial No. 13/081 of the CATALYTICWETOXIDATIONSYSTEMSANDMETHODS by name that on April 6th, 2011 submits to, the continuation-in-part application of 259, the latter is the US application serial No. 11/542 of the CATALYTICWETOXIDATIONSYSTEMSANDMETHODS by name that on October 3rd, 2006 submits to, 675(is now United States Patent (USP) 7,993,588) continuation application case, it is each is incorporated to herein with its entirety for various purposes by reference.

Background of invention

1. invention field

The present invention relates generally to the process of process flow, and relates more specifically to the Catalytic Wet Oxidation system and method for the treatment of wherein unacceptable composition.

2. description of Related Art

Wet oxidation is known technology for the treatment of process flow and is widely used in the pollutent such as destroyed in waste water.The method relates to unacceptable composition at an elevated temperature and pressure by oxygenant, usually from the aqueous phase oxidation of the molecular oxygen of oxygen-containing gas.Organic pollutant can be changed into carbonic acid gas, water and biodegradable short chain organic acid, such as acetic acid by the method.Also can be oxidized inorganic components, comprise sulfide, thiolate and prussiate.As to substituting of burning, wet oxidation to can be used in diversified application using treatment of process streams so as to discharge subsequently, technique internal recycle or as pre-treatment step with the traditional biological treatment facility of supply for advanced treatment (polishing).Catalytic Wet Oxidation has become the effective enhancement to traditional non-catalytic wet oxidation.Catalytic Wet Oxidation method can realize larger destruction usually under lower temperature and pressure and therefore lower cost of capital.Pending aqueous stream is mixed with oxygenant and at an elevated temperature and pressure with catalyst exposure.Heterogeneous catalyst is usually located at (aqueous mixture passes through) or the form of solia particle on bed (its before oxidation with aqueous mixture fusion) thereon.Described catalyzer can be filtered out with recycling from oxidation effluent in wet oxidation unit downstream.

Summary of the invention

According to one or more embodiment, provide Catalytic Wet Oxidation method.The method can comprise the aqueous mixture provided containing the pending unacceptable composition of at least one; Detect the pH value of the aqueous mixture containing the pending unacceptable composition of at least one; Select catalyzer solvable under the pH value detected of this aqueous mixture, wherein this catalyzer and the pH value that detects are selected from: copper under the pH value of about 4 or lower, copper higher than under the pH value of about 13, vanadium under higher than the pH value of about 4.5 and iron lower than under the pH value of about 4; Make the aqueous mixture containing the pending unacceptable composition of at least one with solvable under the pH value detected selected by catalyzer contact at the temperature raised with superatmospheric pressure with oxygenant, to process the unacceptable composition of described at least one; Monitor the pH value of this aqueous mixture; With the pH value keeping this aqueous mixture in the process of this Catalytic Wet Oxidation method, keep soluble form to make described catalyzer.

According to one or more embodiment, this Catalytic Wet Oxidation method comprises the aqueous mixture provided containing the pending unacceptable composition of at least one; Selecting catalyst; Detect the pH value of the aqueous mixture containing the pending unacceptable composition of at least one; Regulate the pH value of the aqueous mixture containing the pending unacceptable composition of at least one, to dissolve selected catalyzer, described pH value is selected from: when catalyzer comprises copper about 4 or lower, when catalyzer comprises copper higher than about 13, when catalyzer comprises vanadium higher than about 4.5 and when catalyzer comprises iron lower than about 4; This aqueous mixture is contacted at the temperature raised with superatmospheric pressure, to process the unacceptable composition of described at least one with oxygenant with selected catalyzer; Monitor the pH value of this aqueous mixture; With the pH value keeping this aqueous mixture in the process of this Catalytic Wet Oxidation method, keep soluble form to make selected catalyzer.In one or more embodiment, selecting catalyst comprises the catalyzer selecting to be present in this aqueous mixture.According to some embodiment, adjust ph comprises use alkali metal hydroxide.

According to one or more embodiment, make described aqueous mixture and selected catalyst exposure before heating.In various embodiments, before pressurization, make this aqueous mixture and selected catalyst exposure.In certain embodiments, this aqueous mixture is oxidized in a continuous process.In at least one, the method comprises supplementary described catalyzer further.In certain aspects, described aqueous mixture and oxidising agent being comprised makes this aqueous mixture contact with oxygen-containing gas.In certain aspects, the method comprises the described catalyzer of recovery further.According to some aspect, reclaim described catalyzer and relate to this catalyzer is precipitated.In various embodiments, described aqueous mixture is made to be oxidized the time being enough to process the unacceptable composition of this at least one.In certain embodiments, superatmospheric pressure is that about 30 normal atmosphere are to about 275 normal atmosphere.According to some aspect, the temperature of rising is about 240 DEG C of critical temperatures to about water.In in other, the temperature of rising is higher than the critical temperature of water.

Accompanying drawing is sketched

Accompanying drawing has no intention to draw in proportion.In the accompanying drawings, each identical or almost identical similar numeral of assembly shown in each figure.For clarity sake, not each assembly can all be marked in each accompanying drawing.Describe preferred non-limiting embodiments of the present invention with reference to the accompanying drawings, wherein:

Fig. 1 is the system diagram of an embodiment according to wet oxidation system of the present invention; And

Fig. 2-4 is herein respectively to the Pourbaix diagram that copper, vanadium and iron are quoted.

Detailed Description Of The Invention

The present invention its application in be not limited in as following explanation set forth or as accompanying drawing in the structure of diagrammatic assembly and the details of layout.The present invention can specialize and can implement in the various modes beyond illustrational mode herein or carry out.

According to one or more embodiment, the present invention relates to one or more system and methods for the treatment of process flow.In typical operation, disclosed system can from community, industry or residential sources receiving process stream.Such as, in the embodiment of this system process waste water, this process flow can from municipal waste water sludge or other extensive sink drainage.Process flow also can be derived from such as food processing plant, chemical processing facilities, gasification projects or paper pulp and paper mill.Process flow can be made through this system by the operation in this system upstream or downstream.

Term used herein " process flow " refers to and can be sent to the aqueous mixture of this system for process.After treatment, this process flow can be sent back to process upstream or can be used as refuse and leave this system.This aqueous mixture generally includes the oxidized unacceptable composition of at least one energy.This unacceptable composition can be any material or compound that are such as intended to for public health, technological design and/or aesthetic consideration remove from this aqueous mixture.In certain embodiments, can oxidized unacceptable composition be organic compound.Some inorganic components, such as sulfide, thiolate and prussiate also can be oxidized.Treat can be shown as from factory or the direct tube shaped keeping container by the source of the aqueous mixture such as slurry of this system process.

According to one or more embodiments of the present invention, it is desirable to destroy one or more specified chemical keys in unacceptable composition or its (one or more) degraded product.Oxidizing reaction oxidable organic pollutant can be changed into carbonic acid gas, water and biodegradable short chain organic acid, the destroy technology of such as acetic acid.One aspect of the present invention relates to the system and method for the oxide treatment for the aqueous mixture containing one or more unacceptable compositions.

In one embodiment, the aqueous mixture wet oxidation of the unacceptable composition of at least one will be comprised.This aqueous mixture is enough to oxidizing the time period processing the unacceptable composition of this at least one at the temperature raised and superatmospheric pressure.This oxidizing reaction can destroy the integrity of one or more chemical bonds in unacceptable composition substantially.Term used herein " destroys " destruction being defined as at least about 95% substantially.Method of the present invention is applicable to process the oxidized any unacceptable composition of energy usually.

Disclosed wet oxidation method can be carried out in the wet oxidation unit of any known intermittent type or continous way that are suitable for compound to be oxidized.Usually, in such as Fig. 1, aqueous phase oxidation is carried out in exemplary display Continuous Flow wet oxidation system.Any oxygenant can be used.This oxygenant normally oxygen-containing gas, such as air, oxygen-rich air or basic pure oxygen.Term used herein " oxygen-rich air " is defined as the air of the oxygen content being greater than about 21%.

Also with reference to figure 1 in typical operation, the aqueous mixture from the source being shown as storage tank 10 flows to high-pressure pump 14 through conduit 12, and this aqueous mixture pressurizes by it.The oxygen-containing gas through pressurizeing that this aqueous mixture and compressor 16 are supplied mixes in conduit 18.This aqueous mixture flows through heat exchanger 20, is heated the temperature of initiated oxidation at this.Then incoming mixture through heating enters reactor vessel 24 at entrance 38 place.Wet oxidation reaction normally heat release, and the temperature of this mixture can be brought up to desirable value by reaction heat further that generate in the reactor.Major part oxidizing reaction occurs in reactor vessel 24, and it provides the residence time of the degree of oxidation be enough to needed for realization.Then the conduit 26 controlled via the control valve 28 that is stressed through the aqueous mixture of oxidation and the gaseous mixture of deoxidation leaves reactor.The effluent through oxidation of heat is through over-heat-exchanger 20, and the original aqueous mixture be transfused to this its and gaseous mixture cool.Effluent mixture through cooling flows to separator vessel 32 through conduit 30, at this separating liquid and gas.This liquid efflunent leaves separator vessel 32 through bottom conduit 34, and waste gas is discharged through upper catheter 36.According to the requirement that it forms and is discharged in air, may need at this waste gas of downstream flue gas processing unit for processing.Effluent through wet oxidation can be discharged in the biological treating equipment for advanced treatment usually.Also this effluent can be circulated to be processed further by this wet oxidation system.

Usually to the oxygen-containing gas of this system supply abundance to keep the residual oxygen in wet oxidation system off gas, and the gaseous tension of superatmospheric pressure is enough to water to be held in liquid phase under selected oxidizing temperature usually.Such as, the minimum system pressure at 240 DEG C is 33 normal atmosphere, and the minimum pressure at 280 DEG C is 64 normal atmosphere, and the minimum pressure at 373 DEG C is 215 normal atmosphere.In one embodiment, this aqueous mixture is oxidized under about 30 normal atmosphere to about 275 atmospheric pressure.This wet oxidation method lower than 374 DEG C, i.e. can operate under the high temperature of the critical temperature of water.In certain embodiments, this wet oxidation method can operate under overcritical high temperature.The residence time of aqueous mixture in reaction chamber should be enough to the degree of oxidation needed for realization usually.In certain embodiments, the residence time is about 1 little of about at most 8 hours for being greater than.In at least one embodiment, the residence time is at least about 15 minutes to about at most 6 hours.In one embodiment, by this aqueous mixture oxidation about 15 minutes to about 4 hours.In another embodiment, by this aqueous mixture oxidation about 30 minutes to about 3 hours.

According to one or more embodiment, wet oxidation method is Catalytic Wet Oxidation method.By catalyzer mediation (mediate) this oxidizing reaction.Aqueous mixture containing the pending unacceptable composition of at least one usually at the temperature raised and superatmospheric pressure with catalyzer and oxidising agent.The catalyzer of significant quantity can be enough to the total failure removal efficiency improving speed of reaction and/or improve this system usually, reduces chemical oxygen demand (COD) (COD) and/or total organic carbon (TOC) with comprising enhancing.Catalyzer also can be used for the overall energy requirement reducing this wet oxidation system.

In at least one embodiment, this catalyzer can be any transition metal of periodictable V, VI, VII and VIII.In one or more embodiment, this catalyzer can be such as V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ag or their alloy or mixture.This transition metal can be element or be present in compound, such as, in metal-salt.In certain embodiments, transition-metal catalyst is vanadium.In other embodiments, transition-metal catalyst is iron.Going back in other embodiments, transition-metal catalyst is copper.

Catalyzer can be added in aqueous mixture any point in wet oxidation system.Catalyzer can be mixed with aqueous mixture.In one embodiment, catalyzer can be added to in the aqueous mixture source of wet oxidation unit feed as shown in fig. 1, wherein catalyst source 40 is fluidly connected on storage tank 10.In certain embodiments, catalyzer directly can be added in wet oxidation unit.In other embodiments, also before heating and/or pressurization, catalyzer can be fed in aqueous mixture.

Going back in other embodiments, catalyzer can be there is in pending process flow.The aqueous mixture being supplied to oxidation unit can contain catalytic material.Such as, treating transition metal to be there is in by the waste streams of this Catalytic Wet Oxidation system process.Aqueous slurries, such as can containing serving as the metal of catalyzer containing those of volatile organic carbon.Such as, this aqueous mixture can be the slurry of gasification byproducts.

According to one or more embodiment, catalyst soluble in aqueous mixture to strengthen wet oxidation method.When for relating to catalyzer, term used herein " solvable " refers to that catalytic amount that this catalyzer dissolves completely or dissolves is enough to cause or accelerate the reaction for process needed for implementing to describe in method and system as disclosed herein in catalysis.Usually, the characteristic of aqueous mixture can affect the solubleness of catalyzer in this aqueous mixture.Such as, the pH value of pending aqueous mixture can affect the solubleness of special catalyst in this aqueous mixture.

In certain embodiments, selecting catalyst can be carried out based on the characteristic of aqueous mixture.As shown in fig. 1, wet oxidation system can comprise the sensor 50 being configured to the characteristic detecting pending aqueous mixture.In certain embodiments, sensor 50 can be the pH sensor of the pH value being configured to detect this aqueous mixture, and the catalyzer can selecting for this wet oxidation method based on the pH value detected of this aqueous mixture.

For various catalyzer, the relation between solubleness and pH value well known to a person skilled in the art.Potential-pH equilibrium diagram is constructed to various catalyzer-aqueous systems and how it can easily obtain with reference to their those skilled in the art for being familiar with.Such as, providing copper, vanadium and iron respectively in Fig. 2-4 can available from Pourbaix, M.M., the reproduction being commonly referred to as Pourbaix diagram of TheAtlasofElectrochemicalEquilibriainAqueousSolutions, NationalAssociationofCorrosionEngineers:Texas1974.

According to one or more embodiment, catalyzer solvable under the pH value detected can be selected to strengthen wet oxidation method.Therefore with reference to figure 2, if the pH value of the aqueous mixture detected by pH sensor 50 is about 4 or lower or higher than about 13, can to the catalyzer selecting cupric according to the catalyst source 40 of one or more embodiment.Similarly with reference to figure 3, when the pH value detected higher than about 4.5 time, the catalyzer containing vanadium can be selected.With reference to figure 4, when the pH value detected lower than about 4 time, the catalyzer of iron content can be selected.Can use provide except illustrating herein these except other catalyzer.

In other embodiments, also can manipulate one or more characteristics of aqueous mixture to promote that selected catalyzer exists with soluble form by selecting catalyst, thus strengthen wet oxidation method.Such as, can the pH value of aqueous mixture be detected by sensor 50 and regulate it to make selected catalyst dissolution in aqueous mixture.At wet oxidation intrasystem any some place, pH adjusting agent can be added in aqueous mixture, but preferably add catalyzer is dissolved in aqueous mixture in the process of oxidizing reaction.In certain embodiments, can as shown in fig. 1 pH adjusting agent source 60 be fluidly connected on aqueous mixture source 10.PH adjusting agent source 60 can comprise any material or the compound that the pH value of aqueous mixture can be adjusted to desirable value or scope usually, such as acid or alkali.Such as, alkali metal hydroxide can be used for the pH value regulating aqueous mixture.In one embodiment, ammonia can be used for making catalyst dissolution.

Again illustrate that, for various catalyzer, the relation between solubleness and pH value well known to a person skilled in the art.As above discuss, Pourbaix diagram can be provided for determining that wherein selected catalyzer is by the information of pH scope needed for solvable.With reference to figure 2, when selected catalyzer comprises copper, the pH value of aqueous mixture can be adjusted to about 4 or lower or higher than about 13.Similarly with reference to figure 3, when selected catalyzer comprises vanadium, the pH value of aqueous mixture can be adjusted to higher than about 4.5.With reference to figure 4, when selecting the catalyzer of iron content, the pH value of aqueous mixture can be adjusted to the value lower than about 4.

In certain embodiments, this wet oxidation system can comprise for regulating or adjusting this system or system component, such as but not limited to the controller 70 of at least one operating parameter of driver's valve and pump.Controller 70 can as shown in fig. 1 with sensor 50 telecommunications.Controller 70 usually can be configured in response to the pH sensor 50 of the solvable extraneous pH value of predetermined pH of the selected catalyzer of record and generate control signal to regulate the pH value of this aqueous mixture.Such as, controller 70 can provide control signal pH adjusting agent to be added in aqueous mixture source 10 to the one or more valves be associated with pH adjusting agent source 60.

Controller 70 normally based on the device of microprocessor, such as programmable logic controller (PLC) or dcs, its from or to wet oxidation system assembly receive or send input and output signal.Communication network can allow any sensor or signal generation apparatus to be positioned at apart from controller 70 or relative computer system place quite far away, still provides data between which simultaneously.Can by utilizing any suitable technology, those including but not limited to the technology adopting wireless protocols are to produce such communication mechanism.

As the typical operation above with reference to oxidation unit discussed, oxidation reactor downstream from through oxidation aqueous mixture separating liquid effluent.In certain embodiments, catalyzer can be reclaimed by separation method from this liquid efflunent.Such as in certain embodiments, catalyzer can be settled out from effluent stream.In one embodiment, crystallizer can be used to reclaim catalyzer.Then can by catalyst recirculation rewetting formula oxidation system.

According to one or more embodiment, if necessary or desired, second-stage treatment unit 80 by being connected to oxidation reactor vessel 24 downstream processes the liquid efflunent stream through wet oxidation, to remove remaining unacceptable composition and/or the advanced treatment of existence.Second-stage treatment unit 80 can be chemical scrubber, biological scrubber, adsorbent media bed or other unit operation.In certain embodiments, can advanced oxidation step be carried out, comprise with ozone and this wet oxidation effluent of ultraviolet oxidation process.Such advanced oxidation process usually in container or groove or close to envrionment temperature and pressure under carry out.Can determine that the size of second-stage treatment unit 80 is to provide the surface-area conformed to required advanced treatment degree.Or, also this liquid efflunent can be looped back in reactor vessel 24 to process further.According to the requirement that it forms and is discharged in air, also may need at downstream flue gas processing unit for processing waste gas.

The sensor of the concentration detecting targeted odorous composition can be provided for auxiliary control system in the upstream of wet oxidation unit 24 and/or downstream.Such as, sensor can be positioned at conduit 26 place and with controller 70 communication, to measure and/or to control whether liquid efflunent circulation to be sentenced to second-stage treatment unit 80 to meet set environmental legislation.

It should be understood that and can make numerous variations, amendment and improvement to shown system and method.Such as, one or more wet oxidation system can link multiple process flow source.In certain embodiments, this wet oxidation system can comprise the additional sensor for other performance or operational conditions measuring this system.Such as, this system can comprise temperature, pressure drop and flow rate sensor and monitors with subsystem at different positions place.According to one or more embodiment, can make-up catalyst in the process of wet oxidation method.

Present invention contemplates amendment existing utility to transform one or more system or assembly thus to realize technology of the present invention.At least some existing device can be utilized to revise existing wet oxidation system according to one or more embodiments of exemplary discussion herein.Such as, one or more pH sensor can be provided in existing wet oxidation system and the controller according to one or more embodiment as herein described can be implemented, with promoting catalyst solubility.

Function and the advantage of these and other embodiment of the present invention is more fully understood by the following example.These embodiments mean illustrative, and should not be considered to limit the scope of the invention.In the examples below that, compound is processed to destroy key wherein by wet oxidation.

Embodiment

Wet oxidation (autoclave) reactor of bench scale

In the examples below that, in laboratory autoclave, carry out the wet oxidation test of bench scale.The difference of autoclave and full scale systems is that they are batch reactors, and full scale unit can be continuous flow reactor.Autoclave runs usually under the pressure higher than full scale unit, because must add large quantity of air to autoclave, to provide sufficient oxygen reacting duration.The result of autoclave test provides the instruction of Wet Oxidation Process performance, and can be used for the operational conditions of screening wet oxidation method.

Autoclave used is made up of titanium, alloy 600 and Nickel200.The selection of autoclave construction material is based on the composition of wastewater feed material.The autoclave of choice for use has the cubic capacity of 500 or 750 milliliters separately.

The pressurized air of waste water and abundance is loaded to provide residual oxygen (about 5%) excessive after oxidation in autoclave.The autoclave of filling is placed in well heater/vibrator mechanisms, is heated to temperature required (280 DEG C to 350 DEG C) and keeps the required time of about 60 minutes to about 360 minutes at this temperature.

Between heating and reaction period, by monitoring the temperature and pressure of autoclave by computer-controlled data collecting system.Immediately autoclave is taken out from well heater/vibrator mechanisms after oxidation, and be cooled to room temperature with tap water.After the cooling period, pressure and the volume of the waste gas in autoclave space is measured.Analyze the permanent gases in waste gas sample.After effluent gas analysis, autoclave is reduced pressure and opens.From autoclave, take out the effluent through oxidation and be placed in storage vessel.Analysis is imposed to the effluent of a part, and remaining sample is used for rear oxidation process.In order to generate the volume enough for analysis operation and rear oxidation test operation, multiple autoclave test is run to various condition.

Embodiment 1

Adopt the wet oxidation method of homogeneous phase copper catalyst

The wet oxidation test of bench scale is carried out with time of 60 minutes at this temperature, to measure the impact of copper catalyst on acetic acid oxidation under various pH value (pH=2.2,8.1,11.5,12.5 and 13.5) at 280 DEG C.Data rows in table 1 below.

Table 1: from the result of the wet oxidation (WO) of the acetic acid solution of use copper catalyst

Copper catalyst shows highest solubility under the pH value of 2.2 and 13.5.When the pH of the effluent through oxidation is 2.2 and 13.5, the acetic acid realizing about 98% and 88% respectively destroys.This also corresponds to the highest COD and destroys per-cent (96.5%, 90%) and TOC destruction per-cent (96.4%, 88.1%).On the contrary, when the pH of this solution remains in the insoluble pH scope of copper (pH=8.1,11.5 and 12.5), the acetic acid only realizing about 17% to 37% destroys.When copper is soluble, also observes lower COD and destroy per-cent and TOD destruction per-cent.These data show that the solubility of copper improves the oxidation of acetic acid significantly.

Embodiment 2

Adopt the wet oxidation method of homogeneous phase vanadium catalyst

Vanadium is used as homogeneous catalyst to the wet oxidation test carrying out bench scale containing second aqueous acid under two kinds of different pH value.The results are shown in following table 2.

Table 2: from the result of the wet oxidation of the acetic acid solution of use vanadium catalyst

Under oxidative conditions, vanadium is solvable under higher than the pH value of about 4.5.Result shows that, when the pH of solution is 2.6 and vanadium is substantially soluble, the TOC only realizing 2% destroys.Low TOC destroys per-cent and is also associated with the pH value of 2.66.Keeping identical catalyst dosage, temperature and while the time at temperature, when the pH of this solution brings up to 5.3 (making vanadium dissolve), TOC destruction brings up to 17.3%.By the pH of this solution is brought up to 5.3 from 2.66, the destruction of total organic carbon improves about 64%.These data show that the solubility of vanadium improves the oxidation of acetic acid significantly.

Embodiment 3

Adopt the wet oxidation method of homogeneous phase iron catalyst

Under two kinds of different pH value, at 230 DEG C, 150 minutes are tested to the wet oxidation that oxalic acid solution carries out bench scale.Data rows is in following table 3.

Table 2: from the result of the wet oxidation of the oxalic acid solution of use iron catalyst

Under oxidative conditions, iron is solvable under lower than the pH value of about 4.Result shows when using iron catalyst under its insoluble high ph-values (pH=13.6 and 13.7), and oxidation does not strengthen.When the pH of this solution is in the solvable scope (pH=2.6 and 1.7) of iron, the destruction of oxalic acid brings up to about 95% and about 100% respectively.These data show that the solubility of iron improves the oxidation of oxalic acid significantly.

Embodiment 4

Adopt the wet oxidation of the chlorophenol of homogeneous phase iron catalyst

So that time of 90 minutes carries out the iron catalysis of chlorophenol and uncatalyzed oxidation at this temperature at 150 DEG C.Data rows is in following table 4.

Table 4: from the result of the wet oxidation of the chlorophenol of use iron catalyst

These tests show, make TOC destruction bring up to about 57% from about 7% by pH value is down to 2.3 solubleness improving iron catalyst from 2.9.Similarly, COD destroys and brings up to about 68.1% from about 7.4% by the reduction of pH value.These data show, the even slight adjustment of pH value also can improve the efficiency of Catalytic Wet Oxidation method significantly.

Embodiment 5

Adopt the wet oxidation method of homogeneous phase copper catalyst

The wet oxidation test of bench scale is carried out with time of 60 minutes at this temperature, to measure the impact of copper catalyst on acetic acid oxidation under various pH value (pH=2.2,2.9,4.3,4.7,8.1 and 11.5) at 280 DEG C.Data rows is in following table 5.

Table 5: from the result of the wet oxidation (WO) of the acetic acid solution of use copper catalyst

Generally speaking result shows, the solubleness of copper catalyst improves with pH and reduces.In addition, acetic acid destructiveness also improves with pH and reduces.These data confirm the conclusion drawn by embodiment 1 further; Mainly the solubility of copper improves the oxidation of acetic acid significantly.As shown in this embodiment, under wide ph range, this oxidising process is strengthened by the existence of copper catalyst.

Term used herein " multiple " refers to two or more items or assembly.Term " comprises ", " comprising ", " with ", " having ", " containing " and " relating to ", no matter be open-ended term in written explanation or claim etc., namely refer to " including but not limited to ".Therefore, the use of this type of term is intended to comprise the item and equivalent thereof and additional things enumerated thereafter.For claim, only have conventional term " by ... form " and " substantially by ... form " be closed respectively or semienclosed conventional term.

Ordinal number such as " first ", " second ", " the 3rd " etc. is used to modify claim elements in the claims, this itself do not imply a claim elements be better than another any priority, in elder generation's property or order, or the time sequence of implementation method operation, but only as the label that a claim elements with a certain title is distinguished with another key element of (but the using ordinal number) with same names, to distinguish claim elements.

Those skilled in the art will appreciate that parameter described herein and structure are exemplary, and the parameter of reality and/or structure will depend on the embody rule using system of the present invention and technology.Those skilled in the art only use normal experiment just to will be appreciated that the equivalent maybe can determining specific embodiment of the invention scheme.Therefore it should be understood that embodiment described herein only provides by way of example, and in the scope of appended claim and equivalent thereof; Differently the present invention can be implemented with specific descriptions.

Claims (20)

1. Catalytic Wet Oxidation method, it comprises:

Aqueous mixture containing the pending unacceptable composition of at least one is provided;

Detect the pH value of the aqueous mixture containing the pending unacceptable composition of at least one;

Select catalyzer solvable under the pH value detected of described aqueous mixture, wherein said catalyzer and the described pH value detected are selected from: copper under the pH value of about 4 or lower, copper higher than under the pH value of about 13, vanadium under higher than the pH value of about 4.5 and iron lower than under the pH value of about 4;

Make the aqueous mixture containing the pending unacceptable composition of at least one with solvable under the pH value detected selected by catalyzer contact at the temperature raised with superatmospheric pressure with oxygenant, to process the unacceptable composition of described at least one;

Monitor the pH value of described aqueous mixture; With

In the process of described Catalytic Wet Oxidation method, keep the pH value of described aqueous mixture, keep soluble form to make described catalyzer.

2. method according to claim 1, wherein makes described aqueous mixture and selected catalyst exposure before heating.

3. method according to claim 1, wherein makes described aqueous mixture and selected catalyst exposure before pressurization.

4. method according to claim 1, is wherein oxidized described aqueous mixture in a continuous process.

5. method according to claim 1, it comprises supplementary described catalyzer further.

6. method according to claim 1, wherein makes described aqueous mixture and oxidising agent comprise and described aqueous mixture is contacted with oxygen-containing gas.

7. method according to claim 1, it comprises the described catalyzer of recovery further.

8. method according to claim 7, wherein reclaims described catalyzer and relates to described catalyzer is precipitated.

9. method according to claim 1, wherein makes described aqueous mixture be oxidized the time being enough to process the unacceptable composition of described at least one.

10. method according to claim 1, wherein said superatmospheric pressure is that about 30 normal atmosphere are to about 275 normal atmosphere.

11. methods according to claim 1, the temperature of wherein said rising is about 240 DEG C of critical temperatures to about water.

12. methods according to claim 1, the temperature of wherein said rising is higher than the critical temperature of water.

13. Catalytic Wet Oxidation methods, it comprises:

Aqueous mixture containing the pending unacceptable composition of at least one is provided;

Selecting catalyst;

Detect the pH value of the aqueous mixture containing the pending unacceptable composition of at least one;

Regulate the pH value of the aqueous mixture containing the pending unacceptable composition of at least one to dissolve selected catalyzer, described pH value is selected from: when described catalyzer comprises copper about 4 or lower, when described catalyzer comprises copper higher than about 13, when described catalyzer comprises vanadium higher than about 4.5 and when described catalyzer comprises iron lower than about 4;

Described aqueous mixture is contacted at the temperature raised with superatmospheric pressure, to process the unacceptable composition of described at least one with oxygenant with selected catalyzer;

Monitor the pH value of described aqueous mixture; With

In the process of described Catalytic Wet Oxidation method, keep the pH value of described aqueous mixture, keep soluble form to make selected catalyzer.

14. methods according to claim 13, wherein make described aqueous mixture be oxidized the time being enough to process the unacceptable composition of described at least one.

15. methods according to claim 13, wherein said superatmospheric pressure is that about 30 normal atmosphere are to about 275 normal atmosphere.

16. methods according to claim 13, the temperature of wherein said rising is about 240 DEG C of critical temperatures to about water.

17. methods according to claim 13, the temperature of wherein said rising is higher than the critical temperature of water.

18. methods according to claim 13, it comprises supplementary described catalyzer further.

19. methods according to claim 13, wherein select described catalyzer to comprise and select the catalyzer that is present in described aqueous mixture.

20. methods according to claim 13, it comprises the described catalyzer of recovery further.