CN101074120A

CN101074120A - Treatment and resource technology for organic waste water

Info

Publication number: CN101074120A
Application number: CN 200710068887
Authority: CN
Inventors: 李小年; 项益智; 巫晓琼; 孔令鸟; 卢春山; 马磊; 张群峰; 丰枫; 袁俊锋
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2007-05-23
Filing date: 2007-05-23
Publication date: 2007-11-21

Abstract

A technology for treating organic waste water and resources is carried out by taking one or two or above organic waste water of phenol, aniline, toluene, butylenes oxide, cyclohexanol, N,N-dimethyl-formamide, methyl cyanide, methanol, methanol, methane acid etc. as raw materials, reform reacting organic substance with water at 180-350 degree under action of ranikel catalyst and 1-16 M pa and generating hydrogen, methane, carbon dioxide and carbon monoxide. It's cheap and efficient and has continuous or intermittent production.

Description

A kind of new treatment of Organic Wastewater and resource technology

(1) technical field

The present invention relates to a kind of treatment process and resource technology of industrial organic waste water, be particularly related to and contain phenol, aniline, toluene, tetrahydrofuran (THF), hexalin, N, the processing of the organic waste water of one or both in dinethylformamide, acetonitrile, methyl alcohol, ethanol, the formic acid or two or more organic matters and the technology of resource utilization.

(2) background technology

Water is Source of life, is basic substance human and other all biological existences and development, also is the important and valuable resource of socio-economic development.Along with expanding economy and Increase of population, the shortage of water resources has become the outstanding environmental problem of contemporary society.China is 2200 cubic metres of own water amounts per capita, and 1/3rd of not enough world average level is one of country that lack of water is the most serious in the world; And process water accounts for 20%, and the average water consumption of major industrial product is than developed country high tens times even hundreds of times, the anxiety of not only having aggravated water, and produce the large amount of sewage contaminate environment." national Environmental statistics communique in 2005 " according to State Environmental Protection Administration's issue shows that 2005,524.5 hundred million tons of national wastewater emission amounts increased by 8.7% than the last year.Wherein discharged volume of industrial waste water is 243.1 hundred million tons, increases by 10.0% than the last year.The industrial pollution source contaminated wastewater is administered 133.7 hundred million yuan of investments, increases by 26.6% than the last year." water pollution control and improvement " is put into one of 16 great special topics of National Program for Medium-to Long-term Scientific and Technological Development.Therefore, carry out sewage disposal research and have important theory and practical significance.Existing treatment of Organic Wastewater technology is divided into biologic treating technique, chemical treatment method and materialization treatment technology three classes roughly:

Biological treatment is one of major technique of purification of waste water, has characteristics such as economically feasible, non-secondary pollution.The main method of biological treatment high concentrated organic wastewater has aerobic, anaerobism and enzyme biologic treating technique and fermentation engineering etc.

Activated sludge process (Activated sludge) is traditional aerobe treatment technology, at first uses in Britain in 1914.Its principle of work is: by the aeration oxygen supply, promote microorganism growth to form active sludge in organic waste water, utilize absorption, oxygenolysis, cohesion and the settling property of the active sludge organic pollutant in purifying liquid waste.In the treating processes, organic degradation is absorption and the oxidative decomposition capacity that relies on active sludge, and it then is cohesion and the settling property that utilizes active sludge that water-mud separates.Biomembrance process (Biofilm techniques) also is a kind of of aerobe treatment technology, it adds the carrier of medium (filler) as microorganic adhesion in the reactor of handling waste water, in the decomposing organic pollutant process, microorganism is growth and breeding on the surface of medium, progressively form muciform film, then, utilize this microbial film that anchors at dielectric surface to purify waste water.In the process of decomposing organic pollutant, microbial growth can make film progressively thicken on the carrier, and the formation top layer is aerobic, internal layer is held concurrently oxygen and anaerobic micro-ecological environment, so biomembrance process has certain anaerobic degradation function.Microbial film thickens to a certain degree coming off automatically, forms mud, and residual or new microorganism attached to dielectric surface breeds continued growth, forms new microbial film.Therefore biomembrance process has advantages such as need not mud refluxes, the biological activity height of film, stable reaction.

The application of (for example fermentation industry, wine brewing, system sauce etc.) has a long history anaerobic digestion process in other field; but developed the automatic purifier of sewage sludge up to Britain Louis Mouras in 1881, this technology just is applied in water environment protection and develops.Subsequently the countries in the world development and design multiple early stage anaerobic device, as septic tank, two-story sedimentation tank, special-purpose digester etc., still be used for that the water drain soiling solution is handled and sewage plant sludge digests today.Rise the seventies in 20th century, anaerobic digestion process causes people's attention owing to have both the two-fold advantage of production capacity and less energy-consumption, then develop and develop the anaerobic reactor of large quantities of similar aerobic degradation technology, adhere to expanded bed (AAFEB), anaerobe rotating disk (ABRD) and anaerobic baffled reactor (ABR) etc. as anaerobic filter (AF), upflow anaerobic sludge blanket process (UASB), anaerobic fluidized bed (AFB), anaerobism.The common feature of novel anaerobic reactor is big (20～60kgVSSm) relative with the reaction times (HRT) short (foreshorten to tens of hours by original a couple of days, tens of sky, even a few hours) of organic loading.In recent years, anaerobism The Application of Technology scope has expanded to the processing of multiple worker, farming, aquaculture organic waste water and the sanitary sewage of high, medium and low concentration.The major defect that the anaerobe technology still exists is: cause " aftertreatment " problem owing to effluent quality is difficult to reach direct emission standard.

Generally speaking, microbial method processing organic waste water is at present most popular a kind of.But it is long that biological process has the spawn culture cycle, stability and poor continuity; Each other inhibition in the fermentation using bacteria process, fermentation end products are to the feedback inhibition of bacterium etc.; In addition, there is the organism of many bio-refractories in the organic waste water, makes biological process be difficult to thoroughly effectively handle organic waste water.

Chemical treatment method is that applied chemistry principle and chemical action are converted into innoxious substance with the pollutants in waste water composition, the method that waste water is purified comprises burning method, Fenton oxidation style, ozone oxidation method, catalytic wet oxidation method, photocatalytic oxidation, electrochemical oxidation process etc.

Fenton reagent is meant H ₂O ₂With Fe ²⁺Combination, the H in this system ₂O ₂At Fe ²⁺Katalysis decompose down and produce the extremely strong OH of oxidation capacity, thereby cause organic oxidative degradation.Along with the further investigation of people, find the improvement technology after the introducing Fenton systems such as UV-light, visible light, oxalate, oxygen can significantly be strengthened Fenton reagent to organic oxidative degradation ability, and can reduce H the Fenton reaction system ₂O ₂Consumption, reduce processing cost.The oxidation technology of Fenton class has advantages such as equipment is simple, reaction conditions is gentle, easy to operate, efficient, has application potential in handling poisonous and harmful difficult for biological degradation organic waste water.After H.REisenhauer in 1964 was used for Fenton reagent the research of phenolic waste water processing first, the research of Fenton reagent in wastewater treatment received concern both domestic and external day by day with application.But because hydrogen peroxide costs an arm and a leg, if use Fenton agent treated waste water separately, then cost is too high, so in application in practice, with its pre-treatment or deep treatment method as organic wastewater with difficult degradation thereby, with other treatment processs (as biological process, Coagulation Method etc.) coupling, then can reduce cost for wastewater treatment better, improve processing efficiency again, can widen this The Application of Technology scope.

Ozone is the strong oxidizer that a kind of oxidation capacity is only second to fluorine, atom in the ozone molecule has intensive electrophilic or protophilia, ozone decomposes the nascent oxygen atom that produces and also has very high oxidation activity, ozone is applied in water sterilization as strong oxidizer, and a lot of application examples are also arranged in wastewater treatment process.Adopting the decolouring of ozone oxidation method will contain water-soluble dye wastewaters such as reactive dyestuffs, cationic dyestuff, matching stain, substantive dyestuff almost completely decolours, also can obtain good decolorizing effect to water-fast dispersed dye, but to water-fast dye decolored weak effects such as sulfuration, reduction, coating.The advantage of ozone oxidation method is that oxidation capacity is strong, and the effect of removing pollutent is remarkable, and the residual ozone in the processed waste water easily decomposes, and does not produce secondary pollution.But, use O merely ₃There is O in oxidative treatment waste water ₃Utilization ratio is low, oxidation capacity is not enough and O ₃Problems such as content is low.Development in recent years be intended to improve the correlation combiner technology of ozone oxidation efficient, wherein UV-O ₃, O ₃-H ₂O ₂, UV-O ₃-H ₂O ₂Be proved to be very effective etc. array mode, not only can improve rate of oxidation and efficient, and can oxidation at O ₃The organism that is difficult to oxidative degradation separately as the time spent.

Ultrasonic sonochemistry oxidation style is the efficient treatment technology of organic pollutant that grows up in the later stage eighties 20th century, its principle is that ultrasonic irradiation solution produces high temperature (＞5000K) cavitation bubble and strong oxidizing property material (as OH) makes hardly degraded organic substance complete oxidation degraded with this understanding, non-secondary pollution.Ultrasonic wave is remarkable to dehalogenation, the oxidation effectiveness of halide-containing, chlorophenol, chlorobenzene, CH ₂Cl ₂, CHCl ₃, CCl ₄Deng the final degraded product of chlorinated organics is HCl, H ₂O, CO, CO ₂Deng.Ultrasonic degradation is also very effective to the denitration base of nitro-compound, and the degraded product of nitrophenols under the ultrasonic wave effect that studies show that of InezHua etc. is NO ^2-, NO ^3-, Resorcinol, carbonate, oxalate etc.Add O ₃, H ₂O ₂, oxygenant such as Fenton reagent will further strengthen the ultrasonic degradation effect, ultrasonic and combinations other oxidation style are present research focuses, as US-O ₃, US-H ₂O ₂, US-Fenton, US photochemical method.Compare with other water technology, still there is the problem that treatment capacity is few, expense is high in ultrasonic sonochemistry oxidation style, still belongs to the exploratory stage at present, and its industrial applications also has the solution of still needing of many problems.

Wet oxidation (Wet air oxidation, WAO), claim wet combustion again, it is a kind of efficient ways of handling high concentrated organic wastewater, its ultimate principle is a bubbling air under the condition of High Temperature High Pressure, makes the organic pollutant in the waste water oxidized, has catalyst-free can be divided into wet oxidation (Wet air oxidation by treating processes, be called for short WAO) and Catalytic Wet Oxidation (Catalytic wet air oxidation is called for short CWAO) two classes.The WAO technology is that (bubbling air under 0.5～20MPa) condition makes the macromolecule organic direct oxidation in the waste water be degraded to inorganics or small organic molecule at high temperature (125～320 ℃) high pressure.Studies show that, traditional WAO technology is more effective for the processing of the organic waste water of high density, poisonous and harmful, difficult for biological degradation, but this method is for dysoxidizable organism decomposition condition harshness, technical requirements, investment and working cost to equipment are very high, even under very high temperature, removal effect to some organism such as polychlorobiphenyl, small molecules carboxylic acid is also undesirable, be difficult to accomplish complete oxidation, be not suitable for actual industrial production, the various countries scholar improves continuously and explores this method for many years for this reason.

Catalytic Wet Oxidation (CWAO) method is to add suitable catalyzer in traditional WAO treatment process, thereby reduce the temperature and pressure of reaction, improve oxidative decomposition capacity, accelerate speed of reaction, shorten the residence time, also therefore can alleviate equipment corrosion, reduce working cost.The catalyzer that selection has good chemical performance and mechanical property is the prerequisite that the CWAO method is used.Zhang Qiubo is with Cu (NO ₃) ₂For carrying out wet oxidation, catalyzer handles coal gasification waste water (COD 22928mg/L, phenol mass concentration 7866mg/L) time, through the suitable treatment time, the clearance of phenol, cyanogen, sulphur is near 100%, the COD clearance reaches 65～90%, and the polycyclic aromatic hydrocarbons type organic had tangible Degradation, as combination H ₂O ₂, O ₃When the oxygenant, can further improve the generation speed of free radical, thereby improve waste water treatment efficiency.Wet peroxide oxidation Phenol-Containing Wastewater Treatment such as Fajerwery, total organic carbon has tangible removal under 90 ℃, normal pressure, and the transformation efficiency of phenol reaches more than 90%.But because homogeneous catalyst is to exist with ionic species, difficult recovery and reuse from waste water.Therefore, heterogeneous catalyst is because the superiority in performance and the use becomes the direction that real application research develops.

Supercritical water oxidation (Supercritical water oxidation, SCWO) utilize organism and oxygenant in supercritical water (temperature T＞374 ℃, the characteristic of dissolving each other fully in the pressure P＞22MPa), make organic substance be similar to the complete oxidation of burning, and, make reaction have advantages such as thorough, rapid owing to there is not the restriction of interphase mass transfer.U.S. Huntsman company has set up the civil sewage treatment plant that first hand utilizes the SCWO technology in 1994 at Texas, states such as Germany, Sweden, Spain and Japan have also set up SCWO sewage work in succession, have realized effective processing of national defense industry waste water, air force's industrial waste, alpha-contamination resin, paper-making industrial waste water and sanitary sewage etc.The SCWO technology of China still is in conceptual phase, the fourth Central Military Commission etc. uses the supercritical water oxidation method Phenol-Containing Wastewater Treatment, in intermittent type and flow reactor, studied temperature (400～500 ℃), pressure (25.3～30.4MPa), the influence of residence time Pyrogentisinic Acid clearance.Discovery under the constant situation of other condition (initial phenol concentration is respectively 100mg/L and 180mg/L), with the rising of temperature of reaction and pressure, the prolongation of the residence time, the phenol clearance improves; In the short residence time, the clearance of phenol can reach more than 96%.Introducing catalyzer in the SCWO technology is the focus of Recent study.JianliYu etc. introduce heterogeneous catalyst CuO, Al in SCWO degraded phenol ₂O ₃, 380 ℃ of reaction conditionss, 25MPa, phenol concentration 20mmol/L, oxygen concn 71mmol/L add catalyzer, reaction 8s, and with comparison under the catalyst-free condition, the phenol degradation rate brings up to 90% by 30%.Supercritical water oxidation method because of be swift in response, degree of oxidation thoroughly receives much attention, but owing under special high temperature, high pressure conditions, react, the subject matter that faces is the corrosion of reaction equipment, to reactor material require high, power consumption is big, thereby limited its industrial applications to a certain extent, developing high temperature resistant for a long time, corrosion resistant reactor material is this method heavy industrialization key in application.

Photocatalytic oxidation is to grow up on the basis of photochemical oxidation method, photochemical oxidation is the reaction process that makes the oxidation operation degraded under visible light or action of ultraviolet light, (290～400nm) are very easily absorbed by organic pollutant near-ultraviolet light in the physical environment, the intensive photochemical reaction takes place when having active substance to exist, thereby makes organic matter degradation.But because reaction conditions is limit, the photochemical oxidation degraded is often thorough inadequately, easily produces multiple aromatic series organic intermediate, becomes the problem that photochemical oxidation need overcome.The late nineteen eighties, along with the pay attention to day by day of environmental pollution Control Study, photocatalytic oxidation is applied to the improvement research of gas phase and some difficult degradation pollutents of aqueous phase, and has obtained significant effect.So photochemical catalytic oxidation Pollution abatement technology becomes the research focus very soon, present result of study proves that the principal pollutant that exist in the environment almost can both the photoactivation oxidation style degrade.

In existing chemical treatment method, all also there is certain problem as burning method, Fenton oxidation style, ozone oxidation method, catalytic wet oxidation method, photocatalytic oxidation, electrochemical oxidation process, supercritical water oxidation method, ultrasonic oxidation method etc.Fenton oxidation style and ozone oxidation method cause the increase of processing cost because the oxygenant price is higher; The temperature and pressure that catalytic wet oxidation method and supercritical water oxidation method are handled is all very high, so the process energy consumption is big; Other as photocatalytic oxidation, electrochemical oxidation process and ultrasonic oxidation method etc. owing to combine the intensifying technology of light, electric harmony, range of application has been subjected to certain restriction.However, chemical process still plays an important role in handling bio-refractory organic waste water, handles energy consumption and processing cost by the different technologies coupling is used to reduce.

The physical chemistry treatment technology is meant that pollutants in waste water variation by phase transition in treating processes reaches the treatment technology of removing purpose.Extraction process is handled high concentrated organic wastewater and is not only had advantages such as facility investment is few, easy and simple to handle, and principal pollutant can effective recycling.Abstraction technique has a wide range of applications in high concentrated organic wastewater is handled, the particularly application of pulse extraction, make the effect of extracting of physical extraction technology improve greatly, waste discharge as Juhua Group Corporation Polyamide Fibre Factory, adopt the pulsed sieve plate column of autonomous design, the average quality mark that can make hexanolactam in the polyamide fibre factory waste water drops to 0.85% from 6.35%, about COD decline 50000mg/L.

Waste water reclaiming is meant that the discarded water that will produce and live is through rationally classification and science are fully utilized after handling.Except it is carried out the comprehensive regulation, directly discharging and in addition outside the reuse can be recycled valuable ingredients wherein for trade effluent.So not only solve environmental pollution, and can produce extra economic benefit.It is the good plan of administering industrial wastewater pollution that direct processing combines with resource utilization, also is the trend of the times of social sustainable development.Organic waste water microbial fermentation hydrogen producing technology is an important technology route of organic waste water resource utilization, this technique functions starts from the nineties in 20th century, and progress rapidly, Chinese scholars is to producing the mechanism of hydrogen, the seed selection of bacterium, the physiological ecology of bacterium, the many-sides such as development of biological hydrogen production conversion unit have been carried out big quantity research, have obtained bigger breakthrough.But bio-hydrogen production technology is also very immature, and great majority research all concentrates on pure bacterial studies and the immobilized cell technique, as the screening of discussion hydrogenogens kind and the selection of embedding medium etc.; In addition, bacterial classification adopts photosynthetic bacterium mostly.Also there is the research scale in microbial fermentation and shortcomings such as the hydrogen production potential level is low, produce stabilized hydrogen and poor continuity, the spawn culture cycle is long in addition.

No matter bio-hydrogen production technology research is photodissociation bio-hydrogen production technology or fermentation method bio-hydrogen production technology in China's progress rapidly, and its achievement in research all reaches international standards.As Institute of Microorganism, Academia Sinica, Shanghai plant physiology institute, Shanghai Communications University, East China Normal University, Zhejiang University and China Agricultural University etc., particularly Harbin Institute of Technology has carried out big quantity research in the seed selection of the product hydrogen mechanism aspect the fermenting organism hydrogen producing technology, bacterium, the physiological ecology of bacterium and the many-sides such as development of biological hydrogen production conversion unit, thus make China bio-hydrogen production technology ahead of the curve the property technical field occupied one seat.At present, the research of bio-hydrogen production technology great majority all concentrates on pure bacterial studies and the immobilized cell technique, as the screening of discussion hydrogenogens kind and the selection of embedding medium etc.; In addition, bacterial classification adopts photosynthetic bacterium mostly.The photosynthetic organism that can produce hydrogen comprises photosynthetic bacterium and algae.The more hydrogen yield photosynthetic bacterium of research mainly contains Crimson rhodospirillum at present, rhodopseudomonas, the outer sulphur rhodospirillum of vacuole, the red bacterium of class ball, folder film rhodopseudomonas etc.Photosynthetic bacterium belongs to prokaryotic organism, and the enzyme of catalysis hydrogen production with photosynthetic bacteria mainly is a nitrogenase.Aspect ferment for hydrogen production, mainly comprise butyric acid type ferment for hydrogen production, propionic acid type ferment for hydrogen production, ethanol-type fermentation hydrogen manufacturing and mixed acid fermentation hydrogen manufacturing at present.Mainly there is following problem at present in bio-hydrogen production technology: how (1) shortens the time of hydrogen production with photosynthetic bacteria, improves the efficient that steady and continuous is produced hydrogen, improves the tolerance degree of photosynthetic bacterium to oxygen.(2) fermenting bacteria produces the stability and the continuity of hydrogen.Though utilize the fermented type Hydrogen Production by Bacteria to obtain significant progress in China,, the stability and the continuity problem that produce hydrogen are that the industrialized obstacle of hydrogen is produced in puzzlement always.(3) each other inhibition in the mixt bacteria fermentation and hydrogen production process, fermentation end products are to the feedback inhibition of bacterium etc.There is the common substrate that utilizes of many suitable photosynthetic organisms and fermented type bacterium in the organic waste water, can be implemented in theory when handling waste water and utilize photosynthetic bacterium and fermenting bacteria to produce hydrogen jointly, improve the efficient of producing hydrogen.But find in the actual mechanical process that each other inhibition and fermentation end products makes DeGrain even hydrogen generation efficiency problem on the low side occurs to the existence of the phenomenons such as feedback inhibition of bacterium in the mixt bacteria fermentation and hydrogen production process.(4) miniaturization of hydrogen producer.

(3) summary of the invention

The object of the present invention is to provide a kind of new treatment of Organic Wastewater and the technology of resource utilization, particularly contain phenol, aniline, toluene, tetrahydrofuran (THF), hexalin, N, the processing of the organic waste water of one or both in dinethylformamide, acetonitrile, methyl alcohol, ethanol, the formic acid or two or more organic matters and the technology of resource utilization, utilize chemical treatment method, make on the one hand and handle organic waste water effectively, also realize the hydrogen manufacturing recycling (being converted into fuel gas such as hydrogen, methane and carbon monoxide) of waste water on the other hand.

Technical conceive of the present invention is as follows:

Under the effect of metal catalysts such as Raney Ni, contain phenol, aniline, toluene, tetrahydrofuran (THF), hexalin, N, the organic waste water of one or both in dinethylformamide, acetonitrile, methyl alcohol, ethanol, the formic acid or two or more bio-refractory organic matters and water generation reforming reaction directly are converted into organism gas molecules products such as hydrogen, methane, carbonic acid gas, carbon monoxide.Its mechanism of action is as follows: organic matter adsorbs on catalyzer, and the cleavage reaction that C-C bond rupture and c h bond take place generates the middle species of CHx, CHx further generates hydrogen and carbon monoxide with water generation reforming reaction, carbon monoxide further generates hydrogen and carbonic acid gas with water generation steam conversion reaction, and low-carbon alkanes such as alkylated reaction or F-T reaction generation methane take place between carbon monoxide or carbonic acid gas and the hydrogen simultaneously.

The technical solution used in the present invention is as follows:

With organic waste water is raw material, under the Raney's nickel catalyst effect, under 180～350 ℃ temperature and 1～16MPa pressure, under catalyst action and water generation reforming reaction, generates hydrogen, methane, carbonic acid gas and carbon monoxide by the organic matter in the waste water; The organic matter that contains in the described organic waste water is phenol, aniline, toluene, tetrahydrofuran (THF), hexalin, N, one or both in dinethylformamide, acetonitrile, methyl alcohol, ethanol, the formic acid or two or more mixing.

Above-mentioned treatment process is carried out as follows: organic waste water was pressed 0.7～7.0 hour ^-1Space-time speed join in the reactor, under the effect of Raney's nickel catalyst, under 180～350 ℃ temperature, 1～16MPa pressure, organic matter in the organic waste water and water generation reforming reaction are converted into hydrogen, methane, carbonic acid gas and carbon monoxide; The space-time speed of described liquid is the volume feeding rate of all reactive material mixed solutions that feed intake and the ratio of the stacking volume of described catalyzer in reactor, and described Raney's nickel catalyst consumption is 5～8g.

Described organic total mol concentration is 0.5 * 10 ^-3～0.25mol/L.

Described treatment of Organic Wastewater technology is that organism changes gas phase small molecules product into water generation liquid phase reforming reaction in the waste water under catalyst action.Described producing hydrogen from organic waste water resource technology is an organic waste water generation aqueous-phase reforming hydrogen production reaction, and one goes on foot the hydrogen that makes of highly selective, comprises reforming reaction and two steps of water gas shift reation.

Further, described liquid phase reforming reaction preferable reaction temperature is 220～270 ℃, and preferred reaction pressure is 2.4～5.5MPa.

Further, described liquid phase reforming reaction carries out in the miniature tubular reactor of the fixed bed of 8mm internal diameter.

In the method, described catalyzer recommends to use Raney's nickel catalyst, is commercially available or self-control, the Raney's nickel catalyst that the embodiment of the invention is used prepares as follows: slowly add strong base solution in Nickel Aluminium Alloy Powder, as NaOH solution, also available certainly other strong base solution is as KOH etc.The temperature of strong base solution is preferably in 20～50 ℃, concentration is 15～25%, be warming up to 75～85 ℃ behind reinforced the finishing, and kept 2～3 hours, extracting goes out discharging behind the aluminium in the alumel, leave standstill then, remove the solution after washing to pH value 8～9, promptly get Raney's nickel catalyst, described Nickel Aluminium Alloy Powder is the nickel bronze of arbitrary proportion and mix (the aluminium gold powder content is non-vanishing) of aluminium gold powder, described alkaline consumption depends on the content (mass content of aluminium is less than 5% in the Raney's nickel catalyst that generally prepares) of aluminium in the alloy powder, and recommending the quality proportioning of nickel bronze and aluminium gold powder is 55: 45, and the quality proportioning of Nickel Aluminium Alloy Powder and highly basic NaOH is 1: 2; Water washing process carries out at 70～80 ℃ earlier usually, washes in normal temperature again.Prepared catalyzer will be preserved with dehydrated alcohol.Prepared catalyzer is little to influence of the present invention in the scope of above-mentioned parameter condition variation.

Concrete treatment process of recommending a kind of organic waste water, carry out as follows: adding Raney's nickel catalyst 5～8 grams in fixed-bed reactor, is 0.5 * 10 with total concn ^-3The organic solution of～0.25mol/L was with 0.7～7.0 hour ^-1The liquid hourly space velocity rate join in the reactor, adjusting temperature of reaction is 220～270 ℃, carries out liquid phase reforming reaction under the pressure of 2.4～5.5MPa, generate hydrogen, methane, carbonic acid gas and carbon monoxide through reactor outlet through gas-liquid separator separates.

The present invention, organic phenol, aniline, toluene, tetrahydrofuran (THF), hexalin, N, the transformation efficiency of dinethylformamide, acetonitrile, methyl alcohol, ethanol, formic acid etc. almost reaches 100%, by products such as micro-hydrogenation and hydrogenolysis is only arranged, COD clearance height in the liquid phase; Hydrogen selective is 0.1～100% in the gas phase.

Compared with prior art, beneficial effect of the present invention is embodied in:

Treatment of Organic Wastewater adopts catalysis aqueous phase reforming reaction technology, has handled organic waste water effectively on the one hand, and has been hydrogen with the organic matter transformation in the waste water effectively, has realized the resource utilization of waste water.Simultaneously, hydrogen is important secondary energy, and China consumed 7,900,000 tons of hydrogen in 2005, was only second to U.S.'s (8,200,000 tons) and accounted for 22% of world's total flow.And at present hydrogen is mainly derived from mineral fuel based on Sweet natural gas, will provide a new approach for the source of hydrogen and the alleviation of international energy problem if can utilize organic waste water to produce hydrogen.Suppose: the composition in the organic waste water is 10 ^-3The phenol of mol/L, 1 ton of organic waste water of so every processing can obtain 313.6L hydrogen; And China's discharging 243.1 hundred million tons of trade effluents (organic waste water accounts for 70%) in 2005 are handled these organic waste waters so and can be obtained nearly 5,300,000,000 m ³The hydrogen of (about 470,000 tons); If the hydrogen price can realize economic benefit 10,000,000,000 Renminbi every year by 2 yuan of/cubic metre calculating.Certainly above calculating is a hypothesis, and the composition difference of organic waste water is produced also difference of hydrogen performance.Compare with existing organic waste water resource technology (microbial fermentation product hydrogen), it is strong that technology provided by the invention has the treatment of Organic Wastewater ability, the hydrogen yield advantages of higher.Further, the hydrogen that is produced in the technology of the present invention helps hydrogen and adopts pressure swing adsorption to realize the purpose of separating and purifying owing to has certain pressure.

To sum up, it is simple that the present invention has technological process, and cost for wastewater treatment is low, and processing power is strong, and the characteristics that resource utilization efficient is high can be carried out continuously or batch production.

(4) embodiment

Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto.Raney's nickel (C) type that employed Raney's nickel catalyst provides for the good sharp metal in Hangzhou company limited in the embodiment of the invention.

Embodiment one

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the phenol solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of phenol is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.29 and 0.2 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 27%.

Embodiment two

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the phenol solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.05mL/min, and (the liquid hourly space velocity rate is 0.7 hour to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of phenol is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.14 and 0.1 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 25%.

Embodiment three

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the phenol solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of phenol is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.48 and 0.16 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 43%.

Embodiment four

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the phenol solution that will contain 0.0005mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of phenol is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.25 and 0.07 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 46%.

Embodiment five

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the phenol solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.0MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of phenol is 92%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.47 and 0.15 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 49%.

Embodiment six

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the phenol solution that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.0MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of phenol is 37%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 2.4,0.7 and 0.07 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 45%.

Embodiment seven

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the aniline solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of aniline is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.33 and 0.3 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 21%.

Embodiment eight

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the aniline solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of aniline is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.52 and 0.23 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 39%.

Embodiment nine

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the toluene solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of toluene is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.34 and 0.37 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 19%.

Embodiment ten

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the toluene solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of toluene is 78%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.33 and 0.27 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 24%.

Embodiment 11

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the hexalin solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of hexalin is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.3 and 0.34 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 18%.

Embodiment 12

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the hexalin solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of hexalin is 98%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.35 and 0.32 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 22%.

Embodiment 13

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the hexalin solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.0MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of hexalin is 91%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.53 and 0.24 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 36%.

Embodiment 14

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, will contain the N of 0.001mol/L, dinethylformamide (DMF) solution is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of DMF is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.1 and 0.17 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 13%.

Embodiment 15

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, will contain the N of 0.001mol/L, dinethylformamide (DMF) solution is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of DMF is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.18 and 0.15 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 23%.

Embodiment 16

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, will contain the N of 0.001mol/L, dinethylformamide (DMF) solution is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.0MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of DMF is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.22 and 0.14 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 28%.

Embodiment 17

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the formic acid solution that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of formic acid is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.6 and 0.1 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 60%.

Embodiment 18

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the formic acid solution that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of formic acid is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.7 and 0.09 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 70%.

Embodiment 19

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the formic acid solution that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.0MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of formic acid is 98%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.72 and 0.08 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 77%.

Embodiment 20

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the methanol solution that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and conversion of methanol is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 1.9 and 0.3 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 63%.

Embodiment 21

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the methanol solution that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and conversion of methanol is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 2.2 and 0.2 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 73%.

Embodiment 22

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the methanol solution that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 240 ℃, and reaction pressure 3.3MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and conversion of methanol is 99%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 2.6 and 0.1 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 87%.

Embodiment 23

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the methanol solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 180 ℃, and reaction pressure 1MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and conversion of methanol is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.2 and 0.01 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 90%.

Embodiment 24

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the ethanolic soln that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and ethanol conversion is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 3.5 and 0.6 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 59%.

Embodiment 25

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the ethanolic soln that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and ethanol conversion is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 3.8 and 0.5 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 63%.

Embodiment 26

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the ethanolic soln that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 240 ℃, and reaction pressure 3.3MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and ethanol conversion is 97%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 4.4 and 0.4 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 75%.

Embodiment 27

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the ethanolic soln that will contain 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 220 ℃, and reaction pressure 2.4MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and ethanol conversion is 92%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 4.5 and 0.25 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 81%.

Embodiment 28

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the acetonitrile solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of acetonitrile is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.12 and 0.11 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 22%.

Embodiment 29

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the acetonitrile solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of acetonitrile is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.17 and 0.1 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 31%.

Embodiment 30

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the acetonitrile solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.0MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of acetonitrile is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.2 and 0.09 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 36%.

The embodiment hentriaconta-

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the acetonitrile solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 240 ℃, and reaction pressure 3.3MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of acetonitrile is 99%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.24 and 0.08 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 44%.

Embodiment 32

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the acetonitrile solution that will contain 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 230 ℃, and reaction pressure 2.8MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of acetonitrile is 98%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.26 and 0.07 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 47%.

Embodiment 33

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.25mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 220 ℃, and reaction pressure 2.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 48%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 11.8,17.9 and 29.7 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 14%.

Embodiment 34

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.25mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 240 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 70%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 3.7,30.4 and 39.4 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 3%.

Embodiment 35

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.25mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.8MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 99%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 0.5,44.6 and 39.4 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 0.3%.

Embodiment 36

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.25mol/L is flowed through with the flow velocity of 0.5mL/min, and (the liquid hourly space velocity rate is 7.0 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.8MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 71%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 2.6,150.8 and 204.2 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 0.4%.

Embodiment 37

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.025mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 230 ℃, and reaction pressure 3.03MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 77%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 7.4,2.0 and 5.6 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 47%.

Embodiment 38

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.025mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.6MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 84%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 6.2,2.5 and 5.9 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 38%.

Embodiment 39

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.025mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 255 ℃, and reaction pressure 4.62MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 92%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 6.5,2.8 and 6.4 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 37%.

Embodiment 40

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.025mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 255 ℃, and reaction pressure 5.28MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 86%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 3.3,3.0 and 5.6 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 21%.

Embodiment 41

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.025mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 255 ℃, and reaction pressure 5.68MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 70%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 1.9,2.6 and 4.4 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 16%.

Embodiment 42

Add Raney's nickel catalyst 7 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.025mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.0 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.62MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 99%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 3.2,3.6 and 6.2 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 18%.

Embodiment 43

Add Raney's nickel catalyst 8 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.025mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 0.88 hour to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.64MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 99.1%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 1.5,4.3 and 5.6 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 8.5%.

Embodiment 44

Add Raney's nickel catalyst 7 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.025mol/L is flowed through with the flow velocity of 0.2mL/min, and (the liquid hourly space velocity rate is 2.0 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.6MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 76.6%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 3.0,2.7 and 5.0 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 22%.

Embodiment 45

Add Raney's nickel catalyst 7 grams in fixed-bed reactor, the tetrahydrofuran solution that will contain 0.005mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.0 hours to reactor ^-1), adjusting temperature of reaction is 250 ℃, and reaction pressure 4.6MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the transformation efficiency of tetrahydrofuran (THF) is 98%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 1.3 and 0.6 μ mol/min, the content of carbonic acid gas and carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 36%.

Embodiment 46

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the phenol mixing solutions that will contain the aniline of 0.001mol/L and 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.64 and 0.05 μ mol/min, the content of carbon monoxide and carbonic acid gas are below chromatographic detectability, and the selectivity of hydrogen is 26%.

Embodiment 47

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the toluene mixing solutions that will contain the aniline of 0.001mol/L and 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.66 and 0.67 μ mol/min, the content of carbon monoxide and carbonic acid gas are below chromatographic detectability, and the selectivity of hydrogen is 20%.

Embodiment 48

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the alcohol mixed solution that will contain the methyl alcohol of 0.01mol/L and 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane, carbonic acid gas is respectively in the gas phase: 6,0.7 and 0.01 μ mol/min, the content of carbon monoxide are below the stratographic detectability, and the selectivity of hydrogen is 70%.

Embodiment 49

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the DMF mixing solutions that will contain the formic acid of 0.01mol/L and 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 0.7,0.27 and 0.02 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 50%.

Embodiment 50

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the phenol mixing solutions that will contain the acetonitrile of 0.001mol/L and 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen and methane is respectively in the gas phase: 0.63,0.27 μ mol/min, the content of carbon monoxide and carbonic acid gas are below chromatographic detectability, and the selectivity of hydrogen is 37%.

Embodiment 51

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the aniline mixing solutions that will contain the phenol of acetonitrile, 0.001mol/L of 0.001mol/L and 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 260 ℃, and reaction pressure 4.7MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 1.15,0.49 and 0.02 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 37%.

Embodiment 52

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the DMF mixing solutions that will contain the phenol of methyl alcohol, 0.001mol/L of 0.01mol/L and 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 2.31,0.59 and 0.01 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 49%.

Embodiment 53

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the DMF mixing solutions that will contain the ethanol of aniline, 0.01mol/L of 0.001mol/L and 0.001mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 3.93,1.07 and 0.01 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 48%.

Embodiment 54

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the alcohol mixed solution that will contain the acetonitrile of phenol, 0.001mol/L of aniline, the 0.001mol/L of 0.001mol/L and 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 90%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 4.67,1.1 and 0.03 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 51%.

Embodiment 55

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the formic acid mixing solutions that will contain the acetonitrile of phenol, 0.001mol/L of aniline, the 0.001mol/L of 0.001mol/L and 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 270 ℃, and reaction pressure 5.5MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 90%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 1.67,0.55 and 0.03 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 43%.

Embodiment 56

Add Raney's nickel catalyst 5 grams in fixed-bed reactor, the formic acid mixing solutions that will contain the acetonitrile of phenol, 0.001mol/L of aniline, the 0.001mol/L of 0.001mol/L and 0.01mol/L is flowed through with the flow velocity of 0.1mL/min, and (the liquid hourly space velocity rate is 1.41 hours to reactor ^-1), adjusting temperature of reaction is 350 ℃, and reaction pressure 16MPa, reactor exit collect liquid and carry out quantitative analysis with island functional activities of the body fluid phase chromatogram (FID, area normalization method), and the total organic matter transformation efficiency is 100%; Gas-phase product detects with online gas-chromatography (TCD, external standard method), and the productive rate of hydrogen, methane and carbonic acid gas is respectively in the gas phase: 1.65,0.64 and 0.03 μ mol/min, the content of carbon monoxide are below chromatographic detectability, and the selectivity of hydrogen is 35%.

Claims

1. the treatment process of an organic waste water, it is characterized in that described method is is raw material with organic waste water, under the Raney's nickel catalyst effect, under 180～350 ℃ temperature and 1～16MPa pressure, under catalyst action and water generation reforming reaction, generate hydrogen, methane, carbonic acid gas and carbon monoxide by the organic matter in the waste water; The organic matter that contains in the described organic waste water is phenol, aniline, toluene, tetrahydrofuran (THF), hexalin, N, one or both in dinethylformamide, acetonitrile, methyl alcohol, ethanol, the formic acid or two or more mixing.

2. the treatment process of organic waste water as claimed in claim 1, it is characterized in that described method carries out as follows: the space-time speed of organic waste water by 0.7～7.0 hour-1 is joined in the reactor, under the effect of Raney's nickel catalyst, under 180～350 ℃ temperature, 1～16MPa pressure, organic matter in the organic waste water and water generation reforming reaction are converted into hydrogen, methane, carbonic acid gas and carbon monoxide; The space-time speed of described liquid is the volume feeding rate of all reactive material mixed solutions that feed intake and the ratio of the stacking volume of described catalyzer in reactor, and described Raney's nickel catalyst consumption is 5～8g.

3. method for processing organic wastewater as claimed in claim 1 or 2 is characterized in that described organic total mol concentration is 0.5 * 10 ^-3～0.25mol/L.

4. method for processing organic wastewater as claimed in claim 1 or 2 is characterized in that described reforming reaction is a liquid phase reforming reaction.

5. method for processing organic wastewater as claimed in claim 4 is characterized in that described liquid phase reforming reaction temperature is 220～270 ℃, and pressure is 2.4～5.5MPa.

6. method for processing organic wastewater as claimed in claim 4 is characterized in that described liquid phase reforming reaction carries out in the miniature tubular reactor of the fixed bed of 8mm internal diameter.

7. method for processing organic wastewater as claimed in claim 1, it is characterized in that described Raney's nickel catalyst prepares as follows: in Nickel Aluminium Alloy Powder, slowly add strong base solution, described strong base solution temperature is controlled at 20～50 ℃, concentration is 15～25%, be warming up to 75～85 ℃ behind reinforced the finishing, and kept 2～3 hours, extracting goes out discharging behind the aluminium in the alumel, leave standstill then, remove the solution after washing to pH value 8～9, promptly get Raney's nickel catalyst, described Nickel Aluminium Alloy Powder is the nickel bronze of arbitrary proportion and mixing of aluminium gold powder.

8. method for processing organic wastewater as claimed in claim 7, the mass content that it is characterized in that the aluminium in the described Raney's nickel catalyst is less than 5%.

9. method for processing organic wastewater as claimed in claim 1 is characterized in that described method carries out as follows: adding Raney's nickel catalyst 5～8 grams in fixed-bed reactor, is 0.5 * 10 with total concn ^-3The organic solution of～0.25mol/L was with 0.7～7.0 hour ^-1The liquid hourly space velocity rate join in the reactor, adjusting temperature of reaction is 220～270 ℃, carries out liquid phase reforming reaction under the pressure of 2.4～5.5MPa, generate hydrogen, methane, carbonic acid gas and carbon monoxide through reactor outlet through gas-liquid separator separates.