CN106381165B - A kind of combustible organic plus hydrogen method for upgrading - Google Patents
A kind of combustible organic plus hydrogen method for upgrading Download PDFInfo
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- CN106381165B CN106381165B CN201610925749.6A CN201610925749A CN106381165B CN 106381165 B CN106381165 B CN 106381165B CN 201610925749 A CN201610925749 A CN 201610925749A CN 106381165 B CN106381165 B CN 106381165B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
Add hydrogen method for upgrading, this method the present invention provides a kind of combustible organic include：Combustible organic is carried out plus hydrogen upgrading by two-part hydrogenation system, wherein the logistics comprising combustible organic is made to pass sequentially through concatenated two hydrogenation catalyst beds, the catalyst filled in described two hydrogenation catalyst beds is different.This method effectively can carry out comprehensive upgrading to combustible organic.
Description
Technical field
The invention belongs to hydrogen addition technology fields, and in particular to a kind of combustible organic plus hydrogen method for upgrading, more specifically
Be related to a kind of bio oil plus hydrogen method for upgrading.
Background technology
The increasingly increase of current energy demand and fossil fuel increasingly reduce and people are promoted to tap a new source of energy, bio-oil
(bio oil) is as a kind of regenerative resource because having the advantages that nitrogen, sulfur content are low and carbon dioxide zero discharge receives full generation
Boundary people widely pay close attention to.But bio-oil has the shortcomings that large viscosity, acid value height, high oxygen content, calorific value are low etc. simultaneously, because
And seriously limit its big application range, it is necessary to which the promotion of quality is carried out to it by modified mode.Currently, bio-oil changes
Property method it is very much, include mainly catalytic hydrogenation, catalytic pyrolysis, catalytic esterification, rectifying, steam reforming etc., wherein catalysis plus
Hydrogen is counted as a kind of both economical effective means, because it can significantly improve hydrogen content therein, to improve life
The calorific value of substance oil.
Currently, the annual output of China's domestic waste is up to 1.8 hundred million tons, rubbish annual output is about 440 public affairs per capita in city
Jin, and rapidly increased with the speed more than 10% every year, it is predicted that the year two thousand thirty, Municipal Solid Waste in China annual output are up to
4.09 hundred million tons.The refuse production per capita of big and medium-sized cities, especially megalopolis is relatively high, and it is left that rate of rise reaches 20%
It is right.
If processing and disposition that cannot be appropriate to these rubbish, (heavy metal, cause of disease be micro- for that poisonous and harmful substance therein
Biology etc.) it will be entered in the ecosystem by certain surrounding medium such as soil, air, earth's surface or underground water and form dirt
Dye.This can not only destroy ecological environment, lead to irreversible Ecological Changes, but also can be good for animals and plants safety and the mankind
Health causes damages.
Garbage disposal at present can only reduce waste volumes by burning disposal.It is each that burning disposal method will produce bioxin etc.
The environmentally hazardous polluter of kind, safe garbage incineration equipment price is high, scale of investment is big, and burning disposal can only pass through
Handling is used for maintaining to run, and resin, Plastic account for 10% or so in conventional rubbish, and remaining is exactly kitchen, paper, wood chip etc..
CN102304372A discloses a kind of superheated steam retort of processing organic waste, it includes superheated steam
The components composition such as stove, organic waste retort, steam turbine generator and gas-liquid separator, gas-liquid separator.
CN102606236A discloses a kind of garbage disposal waste heat power generation system with internal steam pipe, includes refuse gasification
Stove and steamer steam electric power generator, wherein steamer steam electric power generator include steam generator, vapour-discharge tube, steamdrum,
Steam turbine and generator, steamdrum, steam turbine and generator are sequentially connected, it is characterised in that：The steam generator is located at rubbish
In rubbish gasification furnace；Steam generator is the cylinder cage structure being made of upper ring pipe, multiple straight tubes and lower ring pipe, Mei Gezhi
The both ends of pipe are connected with upper ring pipe with lower ring pipe respectively；The upper ring pipe is connected to one end of vapour-discharge tube, is steamed
The other end of vapour discharge pipe is connected with steamdrum, and water inlet pipe is communicated on the lower ring pipe.
CN104976621A discloses a kind of domestic garbage pyrolysis gasification oven, furnace body ecto-entad include burn stove outer covering,
Fire brick layer burns furnace internal-lining；Bottom of furnace body is equipped with deslagging component, water-stop component；Upper of furnace body be equipped with air inlet, can
Gas outlet；Bottom of furnace body is equipped with vapor import；Steam outlet is equipped at the top of furnace body；In fire brick layer and burn furnace internal-lining
Between be equipped with a hollow sandwich；The interlayer bottom is connected to bottom in furnace body, the interlayer top and combustible gas outlet；The folder
Air inlet channel is equipped in layer, which is connected to the air inlet set by upper of furnace body, air into
The lower part in gas channel is connected to bottom in furnace body.
CN204325273U discloses a kind of using water vapour as the rubbish plasma gasification stove of gasifying medium, including top
Refuse gasification room and the high-temperature water vapor of lower part occur room, refuse gasification room and high-temperature water vapor occur between being provided between room
Every the water cooling chimney arch of arrangement, refuse gasification room room with high-temperature water vapor and separates by water cooling chimney arch occurs；The high-temperature water vapor hair
The inner wall of raw room circumferentially two plasma torch, the working gas using low temperature water vapour as plasma torch.
CN102746903A discloses that a kind of to be divided into multiple standard destructive distillation to handle house refuse destructive distillation-gasification furnace single
Member is combined into large-scale house refuse destructive distillation-gasification furnace according to the needs of different disposal ability, and standard destructive distillation processing unit is
The retort section and dryer section of rubbish is arranged in cube furnace body, top, is under anaerobic state first rubbish destructive distillation, is divided using rubbish
Dry distillation gas and carbide residue are solved, carbide burns in lower section burning zone generates high temperature, gasifies with water vapour and air work
Agent, the CO that the carbide under the reduction zone condition of high temperature generates burning2And aqueous vapour reducing, gasification gas is generated, is not just generated
Bioxin；The gasification gas of high temperature, the heating of the rubbish of rubbish retort section, destructive distillation, continues to rise dry during rising
The rubbish of section adds drying, and the organic matter in rubbish is changed into clean gas, collects dry distillation gas and gasification gas is utilized,
It realizes Wu bioxin, non-exhaust emission.
WO2011/000513A1 discloses a kind of comprehensive waste treatment system and method comprising combustiblerefuse source makes
With the separator for detaching the combustiblerefuse from recyclable material, for drying the combustiblerefuse to produce
The vacuum desiccator of raw pyrolysis feed and for by the pyrolysis feed pyrolytic to generate the heat of coke and pyrolysis gas
Solve device.
GB2006/002409A discloses a kind of method for handling rubbish, the method includes：(i) (a) gasification step
Suddenly, the gasification step is included in the presence of oxygen and steam handles the rubbish in gasification unit, to generate exhaust gas and charcoal, or
Person (b) pyrolysis step, the pyrolysis step, which is included in pyrolysis unit, handles the rubbish, to generate exhaust gas and charcoal；(ii)
Plasma treatment step, the plasma treatment step include in the presence of oxygen and optionally in the presence of steam wait from
Corona treatment is carried out to the exhaust gas and charcoal in daughter processing unit.
" Fast Pyrolysis of Biomass for Producing Bio-oil ", Zhu Xifeng etc., scientific and technological Leader, 2007,25 (21)：69-75 passes through member
Element analysis and modified oil structural analysis can hold the effect of catalytic hydrogenation on the whole, while in research biomass crude oil
One-component occurs hydrogenation deoxidation reaction and provides good theoretical direction to improve biomass original under the catalytic condition of MoS2
Oily yield.
Above-mentioned document and it is other in the prior art, be usually all to add to bio-oil (such as crop plant biomass oil)
Hydrogen processing lacks and carries out effective plus hydrogen to rubbish charing acquisition combustible organic or bio oil, and it is flammable organic that rubbish carbonizes acquisition
Object has differences with general bio-oil, such as component has differences, and simply cannot indiscriminately imitate or exchange in technique.
Invention content
It is deeply produced with system research, abundant carbonized in conjunction with domestic waste to solve the above problems, the present inventor passes through
The composition of raw combustible organic has carried out comprehensive research in the full-flow process link of entire garbage disposal, has provided following
Technical solution effectively makes the combustible organic carry out adding hydrogen upgrading.
In one aspect of the invention, provide a kind of combustible organic plus hydrogen method for upgrading, this method pass through two-part
Hydrogenation system carries out combustible organic to add hydrogen upgrading, wherein the logistics comprising combustible organic is made to pass sequentially through concatenated two
Hydrogenation catalyst bed, the catalyst filled in described two hydrogenation catalyst beds are different.
The combustible organic is preferably bio oil.The logistics comprising combustible organic, which removes, includes combustible organic
Outside, also include steam.
It is highly preferred that high temperature distillation charing process of the bio oil from rubbish.The rubbish can be urban life
Rubbish.
Catalyst in the hydrogenation catalyst bed can be independently from each other：Inorganic oxide or the iron of silicate load
The nickel-base catalyst of base catalyst or the ferrum-based catalyst of charcoal load, inorganic oxide or silicate load or charcoal load
Nickel-base catalyst or its any mixture.
The combustible organic is obtained by composting high temperature distillation carbonizing treatment method, and this method includes following step
Suddenly：(1) rubbish is packed into rubbish feeding device；(2) rubbish feeding device is made to pass through high temperature distillation carbonizing apparatus；(3) from high temperature
It distills carbonizing apparatus top and takes out gas stream, which includes the combustible organic.
Charcoal substance is obtained from the rubbish feeding device across high temperature distillation carbonizing apparatus.
By the gas stream comprising the combustible organic by two-part hydrogenation system, to will be contained therein flammable
Organic matter carries out plus hydrogen upgrading.
In the high temperature distillation charing process, the rubbish is preferably domestic waste.
Gas stream is taken out from high temperature distillation carbonizing apparatus top preferably in a continuous manner.
High temperature distillation carbonizing apparatus is heated by high temperature anaerobic steam.
The temperature of the high temperature anaerobic steam is preferably 300-600 DEG C.The pressure of the high temperature anaerobic steam is preferably
0.2-1.0MPa。
Preferably, wherein including nitrogen in the high temperature anaerobic steam.It is highly preferred that nitrogen content is 10-80v.%, more
It is preferred that 20-60v.%.
In the present invention, it is preferred to rubbish without any pretreatment.
For the present invention, compared with simple destructive distillation in the prior art, the presence of nitrogen can avoid rubbish from being carbonized
It burns in the process, makes the charcoal of generation that there is higher calorific value.In addition, compared with steam gasification pure in the prior art,
The presence of nitrogen can also increase heat medium calorific value, improve the efficiency of heating surface to improve charing efficiency, while can also save
Steam consumption more importantly by the addition of nitrogen, can provide required catalysis item for the catalysis upgrading of follow-up distillate
Part, such as required vapor partial pressure is adjusted, because excessively high vapour pressure can cause catalysis upgrading to be difficult to effectively carry out, nitrogen adds
Enter the vapor partial pressure that can be reduced in gas stream i.e. distillate.
The inventors discovered that in existing waste steam treatment technology, the composition often having ignored for rubbish has choosing
Steaming conditions are selected to selecting property, the difference of rubbish composition is had ignored, causes garbage treatment efficiency relatively low.The present inventor passes through
Numerous studies select different steaming conditions according to different rubbish compositions, obtain good steam treatment effect.It is special
Not, following high temperature distillation charing process condition is selected：(1) with the total weight of rubbish, organic species in rubbish forms
When content >=80 weight %, the temperature of high temperature anaerobic steam is 300-450 DEG C, preferably 300-400 DEG C；In high temperature anaerobic steam
Nitrogen content is 10-30v.%, preferably 10-20v.%；Residence time in high temperature distillation carbonizing apparatus is 8-12h；(2)
When with the total weight of rubbish, when organic species content 80 weight % of ＜, the temperature of high temperature anaerobic steam is in rubbish composition
450 DEG C -600 DEG C, preferably 500 DEG C -550 DEG C；Nitrogen content in high temperature anaerobic steam is 40-80v.%, preferably 60-
80v.%；Residence time in high temperature distillation carbonizing apparatus is 5-8h.
The study found that the such high temperature distillation carbonization condition of selection, is since plastic, rubber substance is high temperature distillation charcoal
One of the source of bio oil during change, the ingredients such as the rubbish from cooking that compares and wood grass are non-to steam distillation carbonization condition
It is often sensitive, when its content is high, needs to make its decomposition using higher temperature and water vapour, but distill carbonization time and again cannot
It is long, it is otherwise easy to that the bio oil of generation is made to resolve into micro-molecular gas, biological oil yield is caused to reduce, and generate harmful pair
Product.
When organic species content is higher in rubbish, above-mentioned steaming conditions are particularly conducive to generate liquid combustible object
Generation；And organic species content it is relatively low when, be particularly conducive to the generation of charcoal substance.
The two-part hydrogenation system includes concatenated two hydrogenation catalyst beds, i.e. the first catalyst bed and the second catalysis
Agent bed, wherein the first catalyst bed is located at the upstream of the second catalyst bed.
In the particularly preferred embodiment of the present invention, the present inventor passes through numerous studies, develops a kind of energy
Enough effectively to carrying out the catalyst for adding hydrogen upgrading from the bio oil in the gas stream that high temperature distillation carbonizing apparatus top is taken out,
The catalyst is used for the first catalyst bed, and it includes carrier and load active constituent on the carrier, wherein carrier can be with
For Al2O3、SiO2、TiO2, molecular sieve, one or more mixtures in activated carbon, catalytic active component can be Fe2O3With
The mixture of at least two transition metal and at least one noble metal.The transition metal is selected from Ni, Cu, Fe, Ce etc., described
Noble metal is selected from Pt, Pd, Ru etc..
In an especially preferred embodiment, the catalyst of the first catalyst bed can be catalysis shown in following formula
Agent：Ni-Cu-Pd-Co2O3-Fe2O3/ HZSM-5, the wherein molar ratio of Ni, Cu, Pd, Co, Fe are (1-2):(5-10):(0.1-
0.5):(1-2):(10-20) is based on overall catalyst weight gauge, Ni-Cu-Pd-Co2O3-Fe2O3The content of active constituent is 1-
10%, preferably 2-8%, more preferable 5%.HZSM-5 is carrier.Preferably, HZSM-5 is the HZSM-5 of low silica-alumina ratio, such as silicon
Aluminium ratio is less than 15, more preferably less than 10, this is because finding that acid strong HZSM-5 is more advantageous to splitting for bio oil heavy component
Solution, bio oil bottoms are minimum.
The ingredient of bio oil is usually relatively complex, and mainly may include acids, aldehydes, ketone, alcohols, phenols, furans, ester
Class, ethers and a small amount of nitrogenous compound and other multi-functional compounds.Since bio oil thermal stability is poor, acid and corrosivity
By force, water content is high, calorific value is low and is not easy the characteristics such as to dissolve each other with petroleum-based products, therefore bio oil can only realize that primary is answered at present
With for example for heat power equipments such as Industrial Stoves and oil burning boilers, oil product cannot being substituted and directly apply to internal combustion engine or turbine
The burning of machine cannot be satisfied modern high-grade commercial Application.In order to improve bio oil application, need to be transformed into Gao Pin
The liquid fuel of position reaches the requirement of transport fuel, and to realize replacement or partial alternative oil product, this just must be to biology
Oil is modified upgrading, its chemical constituent is made to be converted into hydrocarbon by hydrocarbon oxygen compound.How effectively to bio oil
One of the key for carrying out upgrading is the exploitation of catalyst.
The study found that in the above-mentioned catalyst of the present invention, Niδ+Than conventional Moδ+With higher activity, Ni's makes
With that can obtain C6-C12 hydrocarbon (preferably alkane) with high selectivity, the use of Cu can obtain C16 hydrocarbon (preferably alkane with high selectivity
Hydrocarbon), Ni, Cu while, uses, it has surprisingly been found that it may also be ensured that obtaining a certain amount of C18 and C19 hydrocarbon, surface Ni, Cu's makes
Hydrogenolysis effectively occurs with the C-O keys in bio oil can be made.
It is different from general improving quality of biomass oil, in the gas stream of the present invention, the steam containing higher proportion, therefore
Very high request is proposed to the hydrothermal stability of catalyst.The conventional catalyst for improving quality of biomass oil cannot be used for this
The upgrading of the gas stream of invention.Iron catalyst is to remove a kind of common catalyst of oxygen in plant base material, however iron is catalyzed
Agent meet water when fail, although and palladium catalyst meet water when effectively, the effect of its deoxygenation is not fine, and costly, and
Minimal amount of palladium is added in iron, can get synergistic effect well.Inventor is the study found that the addition of a small amount of palladium contributes to hydrogen
Be covered in the surface of iron in catalyst, reaction made to accelerate, and prevent water blocking from reacting, thus hydrogen consumption it is small, activity, stability and
For selectivity aspect far better than individual iron catalyst, 2 times or more can be improved in catalytic life.
The present inventor also found that the addition of Co advantageously reduces the crystallite dimension of catalytic active component, can through research
Enough be effectively embedding in the duct of HZSM-5 molecular sieves, this for improve catalytic active component activity, selectivity and stabilization
Property has very positive meaning.However, if Co amounts are excessive, Co can cover hydrogenation sites Ni, Cu etc., be urged to reduce
The activity of agent.
Contain more non-aromatic hydro carbons in the bio oil of gas stream, the acid centre on HZSM-5 molecular sieves can
It is effectively aromatic compound by the non-aromatic hydrocarbon conversion.Carboxylic acid in bio oil largely derives from the acetyl of hemicellulose
Base, thermal decomposition product are mainly acetic acid, and HZSM-5 molecular sieves have preferable decarboxylation ability, and the carboxylic acid in bio oil is in molecular sieve
Decarboxylic reaction and deoxygenation occur under catalytic action so that carboxylic acid content is greatly decreased in the bio oil after upgrading.
There is not been reported in prior document for above-mentioned particularly a preferred catalyst, is that the present invention is directed to from garbage reclamation
What the concrete composition feature of gas stream and bio oil targetedly designed, achieve good upgrading effect.
It is prepared by the dipping calcination method that this field routine may be used in the catalyst.Specifically, it weighs according to the above ratio
A certain amount of precursor salt such as Ni (NO3)2、Cu(NO3)2、Pd(NO3)2、Co(NO3)2、Fe(NO3)3(or their hydrate form)
And citric acid, add deionized water dissolving, stir evenly, be made into the solution of a concentration of 0.5-1.5mol/L, weighs a certain amount of
HZSM-5 molecular sieves are put into reaction vessel, and the solution prepared is poured into reaction vessel, are placed in the constant temperature with blender and are added
Heating, stirs 1h-10h at a temperature of 60-120 DEG C, is then placed in 100 DEG C of -150 DEG C of dryings in drying box in deep fat bath apparatus
Obtained catalyst precursor is then placed in 500 DEG C of -800 DEG C of calcining 1h-6h in Muffle furnace, then in H by 12h2In the presence of in
Ni-Cu-Pd-Co is made in reduction activation at 200-300 DEG C2O3-Fe2O3/ HZSM-5 catalyst.
First catalyst bed plus hydrogen upgrading condition be preferably：200-300 DEG C, 1.0-10.0MPa hydrogen pressures, 1-5h；It is more excellent
It is selected as：250 DEG C, 8.0MPa hydrogen pressures, 2h.
For the present invention, the catalyst of the second catalyst bed is preferably the NiMo/ γ-Al vulcanized2O3.The catalyst can
With commercially available acquisition, can also conventionally be made.
Second catalyst bed plus hydrogen upgrading condition be preferably：150-300 DEG C, 1.0-6.0MPa hydrogen pressures, 2-6h；More preferably
For：200 DEG C, 5.0MPa hydrogen pressures, 3h.
For the present invention, the gas stream is preferably substantially free of bioxin.Because of the distillation that heats up under anaerobic state, institute
It, can be with environment protection not will produce the harmful substances such as bioxin.This has prodigious excellent compared to common burning method
Gesture.
Preferably, the high temperature anaerobic steam wherein used in high temperature distillation carbonizing apparatus comes from high pressure through-flow steam oven.
In another aspect of this invention, it is that liquid can to provide the combustible organic through upgrading obtained according to preceding method
Combustion things, the i.e. bio oil through upgrading.Preferably, oxygen content is less than 10 weight % in the liquid combustible object through upgrading, preferably
Less than 5 weight %, more preferably less than 2 weight %.Further, the higher calorific value of the liquid combustible object is more than 60MJ/kg.
In another aspect of this invention, the charcoal class object obtained according to the method for any one of preceding claims is provided
Matter.
Preferably, the charcoal substance is coke.
Preferably, the charcoal substance is semicoke.
Description of the drawings
Fig. 1 is the vertical view of high temperature distillation carbonizing apparatus according to the present invention；
Specific embodiment
With reference to following embodiment and comparative example, the present invention is described in further detail, but the embodiment party of the present invention
Formula is without being limited thereto.
Embodiment 1
The house refuse that garbage compression transfer station is occupied from five tunnel of Haidian District, Beijing City is chosen, the composition of the rubbish is through inspection
It surveys as shown in table 1 below：
Table 1：Domestic waste is at being grouped as
High temperature distillation charing is carried out to above-mentioned rubbish by following steps：(1) rubbish is packed into rubbish feeding device；(2)
Rubbish feeding device is set to pass through high temperature distillation carbonizing apparatus；(3) gas stream is taken out from high temperature distillation carbonizing apparatus top.It is described
High temperature distillation carbonizing apparatus is heated by high temperature anaerobic steam, and the temperature of high temperature anaerobic steam is 355 DEG C, and high temperature anaerobic steams
Nitrogen content in vapour is 12v.%, and processing average time is 9.0 hours.
Gas stream carries out hydrogenation deoxidation upgrading using two-part hydrogenation system, wherein gas stream is made to pass sequentially through series connection
The first hydrogenation catalyst bed and the second hydrogenation catalyst bed.Upgrading catalyst used in first catalyst bed is Ni-Cu-Pd-
Co2O3-Fe2O3/ HZSM-5, the wherein molar ratio of Ni, Cu, Pd, Co, Fe are 2:8:0.15:1.5:15, it is based on overall catalyst weight
Gauge, Ni-Cu-Pd-Co2O3-Fe2O3The content of catalytic active component is 5%, and it is 250 DEG C to add hydrogen upgrading condition, 8.0MPa hydrogen
Pressure, 2h.Upgrading catalyst used in second catalyst bed is NiMo/ γ-Al2O3(derive from the petrochemical industry research of sinopec Fushun
Institute), the hydrogen upgrading condition that adds of the second catalyst bed is：200 DEG C, 2.0MPa hydrogen pressures, 3h.It is obtained through upgrading by this method
Bio oil, that is, combustible organic, the combustible organic are in a liquid state at normal temperatures.
Oxygen content in bio oil through upgrading is 1.9wt.%, and the catalyst life used in the first catalyst bed is about
720h, the catalyst life used in the second catalyst bed is about 540h.
Comparative example 1
The comparative example uses single filling NiMo/ γ-Al with differing only in for embodiment 12O3Catalyst bed.Through
Oxygen content in the bio oil of upgrading is 9.9wt.%, and the catalyst life used in catalyst bed is about 320h.
By above-described embodiment and comparative example clearly it can be seen from the present invention method the bio oil of upgrading can be made to have
Significantly lower oxygen content, this shows to achieve preferable hydrogenation deoxidation upgrading effect, to make fuel have higher calorific value
And stability, the catalyst life of this additional hydrogen upgrading also significantly improve.
This written description discloses the present invention, including optimal mode using example, and also enables those skilled in the art
It manufactures and using the present invention.The present invention can patentable scope be defined by the claims, and may include this field skill
Other examples that art personnel expect.If this other examples have not different from the structural elements of the literal language of claims
Element, or if this other examples include with equivalent structure element of the literal language of claims without substantial differences,
Then this other examples are intended within the scope of claims.In the case where inconsistent degree will not be caused, by reference to
It will be incorporated herein in place of all references referred to herein.
Claims (7)
1. a kind of combustible organic adds hydrogen method for upgrading, this method to be added combustible organic by two-part hydrogenation system
Hydrogen upgrading, wherein the logistics comprising combustible organic is made to pass sequentially through concatenated i.e. the first catalyst bed of two hydrogenation catalyst beds
With the second catalyst bed, the first catalyst bed is located at the upstream of the second catalyst bed, is filled in described two hydrogenation catalyst beds
Catalyst it is different；
Catalyst in first catalyst bed is catalyst shown in following formula：Ni-Cu-Pd-Co2O3-Fe2O3/ HZSM-5, wherein
The molar ratio of Ni, Cu, Pd, Co, Fe are (1-2):(5-10):(0.1-0.5):(1-2):(10-20) is based on total catalyst weight
Meter, Ni-Cu-Pd-Co2O3-Fe2O3The content of active constituent is 1-10%, and HZSM-5 is carrier；
Catalyst in second catalyst bed is the NiMo/ γ-Al of vulcanization2O3Catalyst；
First catalyst bed plus hydrogen upgrading condition be preferably：200-300 DEG C, 1.0-10.0MPa hydrogen pressures, 1-5h；
Second catalyst bed plus hydrogen upgrading condition be preferably：150-300 DEG C, 1.0-6.0MPa hydrogen pressures, 2-6h.
2. according to the method described in claim 1, the wherein described combustible organic is bio oil.
3. according to the method described in claim 2, high temperature distillation charing process of the wherein described bio oil from rubbish.
4. according to the method described in claim 3, the wherein described rubbish is domestic waste.
5. the charing of method according to claim 3 or 4, wherein high temperature distillation is heated by high temperature anaerobic steam to carry out.
6. according to the method described in claim 5, the temperature of the high temperature anaerobic steam is 300-600 DEG C.
7. according to the method described in claim 6, including nitrogen in the wherein described high temperature anaerobic steam.
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