CN110252419A - A kind of method and its application reducing catalytic reforming catalyst carbon distribution deactivation rate - Google Patents
A kind of method and its application reducing catalytic reforming catalyst carbon distribution deactivation rate Download PDFInfo
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- CN110252419A CN110252419A CN201910624173.3A CN201910624173A CN110252419A CN 110252419 A CN110252419 A CN 110252419A CN 201910624173 A CN201910624173 A CN 201910624173A CN 110252419 A CN110252419 A CN 110252419A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A kind of method and its application reducing catalytic reforming catalyst carbon distribution deactivation rate, belong to the preparation method technical field of hydrogen.The method of the reduction catalytic reforming catalyst carbon distribution deactivation rate, for during water vapour catforming, in catalytic reforming tar, hydrogen peroxide is added in catalytic reforming reaction object vapor, wherein, the additional amount of hydrogen peroxide accounts for the mass percent of vapor and dioxygen aqueous mixtures are as follows: 0%-10%, when for 0%, for interval addition hydrogen peroxide.This method can be such that the carbon deposition rate of catalytic reforming catalyst reduces, and not increase the energy consumption of catalytic reforming process additionally, and do not influence density of hydrogen and yield.
Description
Technical field
The present invention relates to the preparation method technical fields of hydrogen, are specifically related to a kind of reduction catalytic reforming catalyst carbon distribution
The method and its application of deactivation rate.
Background technique
Hydrogen is a kind of ideal energy, and a kind of important industrial chemicals.Currently, hydrogen is mainly by natural gas, light
Matter alkane and naphtha water vapour catforming are made, and coal gasification also has certain applications.With increasingly depleted, the people of fossil fuel
More attentions are turned into the biomass material hydrogen manufacturing that renewable, reserves are big, environmental-friendly.
Biomass Catalytic Gasification hydrogen manufacturing is to generally believe one of biomass hydrogen preparation technology of most commercial promise, pass through by
Biomass is placed under high temperature, through a series of thermal chemical reactions such as pyrolysis, hydrolysis, oxidation, reduction, is generated with H2、CO2、CO、CH4For
Main product gas is converted by steam reformation, aqueous vapor later and the processes such as the separation and compression of PSA hydrogen prepares High Purity Hydrogen
Gas.But by-product is inevitably generated during pyrolytic gasification --- tar.It is a kind of liquid that dark brown is thick
Body, primary chemical composition includes two classes: first is that the aromatization based on benzene,toluene,xylene, phenol, naphthalene, styrene, indenes
Close object；Second is that a small amount of oxygen-containing, nitrogenous and sulfur-bearing compound.The presence of tar causes huge danger to entire gasification system
Evil: (1), hydrogen yield is reduced；(2), the tar of condensed state influences the normal operation of system and device after condensing；(3), harmful to human
Health and environment；(4), the further utilization of hydrogen gas product is hindered.
In order to reduce the harm of tar, the method for removing tar removing at present mainly has two major classes: one is divided into wet process and does
The physical cleaning method of method, two are divided into the heat chemistry purification method of thermal cracking and catalytic reforming.
Physical cleaning method passes through physical means and gets rid of tar, but either dry method or wet process is only by tar from gas
Inversion of phases is liquid phase or solid phase, is the phase conversion of tar rather than really removes it.
Thermalization chemical purification then refers to occurs series of chemical for tar in a certain temperature conditions, by macromolecular
Tar conversion be small molecule gaseous products.This method can not only reduce tar content, recycle contained by tar
Energy, and it has been inherently eliminated the influence of tar.
Pyrolysis method refers to directly is pyrolyzed tar at very high temperatures, this process can lead to the tar of macromolecular
Cross the gaseous compound that the reactions such as scission of link dehydrogenation, de- alkyl are converted into small molecule.But this method required temperature is very high, generally
Preferable effect could be obtained at 1000-1200 DEG C.However during production application, this temperature is more difficult to be reached
It arrives, and economically also unreasonable.
Catalytic reforming is that reaction temperature is down to 700-900 DEG C under the effect of the catalyst to be obtained with preferable tar
Transformation efficiency.Compared with thermal cracking, the reaction temperature of catalytic reforming is within the tolerance range of some reactor materials, and energy
Consumption is greatly improved, therefore is considered as the most economical method of tar removing.
Since nickel-base catalyst is cheap compared to noble metal platinum, compared to natural crystal and other metal active constituents activity
With selective height, therefore, nickel-base catalyst is industrial most widely used reforming catalyst.However, Ni-based reforming catalyst
It faces carbon distribution and inactivates this key technology difficulty.
Domestic and international researcher is when solving this problem, there are two ways to commonly using, first is that increasing vapor and tar
Mass ratio, second is that by adjusting the Nomenclature Composition and Structure of Complexes of catalyst.However, increasing the mass ratio of vapor and tar will increase greatly
Adding system energy consumption, the chemical composition and structure for adjusting catalyst are also extremely limited to the carbon deposition rate for reducing catalyst.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of reduction catalytic reforming catalyst carbon distribution deactivation rates
Method and its application, this method reduces biomass catalyzing reformation by adding hydrogen peroxide in reforming reactants vapor
The carbon distribution deactivation rate of reforming catalyst in the process.
The method of a kind of reduction catalytic reforming catalyst carbon distribution deactivation rate of the invention, in water vapour catforming mistake
Cheng Zhong adds hydrogen peroxide in catalytic reforming reaction object vapor, wherein the additional amount of hydrogen peroxide in catalytic reforming tar
Account for the mass percent of vapor and dioxygen aqueous mixtures are as follows: 0%-10%, when for 0%, for interval addition hydrogen peroxide.
The additional amount of the hydrogen peroxide accounts for vapor and the mass percent of dioxygen aqueous mixtures is preferred are as follows: 2%-4%.
When for interval add hydrogen peroxide, the intermittent time≤10min.
During water vapour catforming tar, catalytic reforming temperature is 650-950 DEG C, preferably 700-900 DEG C.
During water vapour catforming tar, molar ratio (S/C)=(2-3): the 1 of carbon in vapor and tar.
The tar is the by-product of biomass gasifying hydrogen making, the by-product of biomass cracking hydrogen manufacturing, hydrogen production from coal gasification
By-product, one of the by-product of coal cracking hydrogen production.
The by-product of the biomass gasifying hydrogen making is that the raw material of biomass passes through 700-900 DEG C of high-temperature gasification, obtains
Room temperature not condensable liquid product be tar.
The raw material of the biomass is biomass material commonly used in the art, specifically selects agricultural wastes, forestry useless
One or more of gurry, forestry processing Litter, water plant and energy crop.
During the water vapour catforming, the catalytic reforming catalyst of use is preferably nickel-base catalyst, more excellent
It is selected as Z409 catalytic reforming catalyst.
A kind of application of the method for reduction catalytic reforming catalyst carbon distribution deactivation rate of the invention is used for gasification of biomass
The catalytic reforming process of hydrogen manufacturing, the catalytic reforming process of biomass through pyrolysis hydrogen manufacturing, hydrogen production from coal gasification catalytic reforming process, coal
One of the catalytic reforming process of thermal cracking hydrogen manufacturing, gas water steam catalytic reforming process process.
The catalytic reforming process of the biomass gasifying hydrogen making, includes the steps that are as follows:
(1) catalytic reforming catalyst is filled in fixed bed tube furnace；
(2) fixed bed tube furnace is purged using nitrogen, so that being inert atmosphere in fixed bed tube furnace；
In the step (2), the flow and purge time of nitrogen are according to the specification and catalytic reforming of fixed bed tube furnace
The filling height of catalyst determines, preferably, the flow velocity of nitrogen is 10-25m/ according to pipeline specifications in fixed bed tube furnace
S, purge time are preferably 20-60min.
(3) fixed bed tube furnace is warming up to 650-950 DEG C of reaction temperature, after temperature reaches reaction temperature and stablizes,
Nitrogen flow is adjusted to 0m/s；
(4) product after the mixture and gasification of biomass of mixed hydrogen peroxide according to the ratio and water is passed through fixation
In bed tube furnace, catalytic reforming is carried out；Wherein, in the mixture of hydrogen peroxide and water, hydrogen peroxide accounts for water and dioxygen aqueous mixtures
Mass percent is 0-10%, and when for 0%, interval is passed through the mass percent that hydrogen peroxide accounts for and is greater than 0% less than or equal to 10%
Hydrogen peroxide and water mixture, wherein in molar ratio, water: carbon=(2-3): 1 in tar.
A kind of method and its application of reduction catalytic reforming catalyst carbon distribution deactivation rate of the invention, principle foundation
It is: is judged according to chemical bond energy data, the hydrogen atom in tar is easiest to fracture and is precipitated.Tar is substantially by hydrocarbon two kinds of element groups
At once hydrogen atom is precipitated, component will be tended to form the higher tar component of aromaticity.If the up to certain journey of aromaticity
Degree carbon distribution is formed.While the more satisfactory process of catalytic reforming is that hydrogen atom is precipitated, the aromatic rings fracture of tar is best
All C-C keys are also all opened on chain, and carbon atom generates CO or CO in conjunction with the oxygen atom that oxygen atom donor provides2, such ability
Avoid the generation of carbon distribution.But catalytic reforming catalyst carbon distribution is biomass coke tar catalytic reforming, gas water steam catalytic weight
The Key technique problem of the technologies general character such as whole, coal tar catalytic reforming.Judgement may be oxygen atom donor vapor as a result,
Formation oxygen atom difficulty is larger, or the oxygen atom activity formed is not high.Therefore, it is higher will to introduce activity by the present invention in vapor
Hydrogen peroxide to promote carbon to convert to gas direction to reduce the carbon distribution deactivation rate of catalytic reforming catalyst.Pass through experiment
Research finds that hydrogen peroxide introduces excessive, and the available gas component that gasification of biomass generates will reduce.Thus, optimize dioxygen
The introduction volume of water and the occasion of introduction for being continuously introduced into low concentration or being introduced with interval mode, had both met the need for the carbon that disappears in this way
It asks, and is unlikely to excessive reduction gaseous product and effectively forms.
A kind of method and its application of reduction catalytic reforming catalyst carbon distribution deactivation rate of the invention, actively progress is imitated
Fruit is:
1) method of the invention is used, the carbon deposition rate of catalytic reforming catalyst reduces.
2) method of the invention is used, does not increase the energy consumption of catalytic reforming process additionally.
3) method of the invention is used, density of hydrogen and yield do not reduce.
Detailed description of the invention
Fig. 1 is the apparatus structure schematic diagram that catalytic reforming catalyst carbon distribution deactivation rate is measured in the present invention, in which: 1: nitrogen
Gas cylinder；2: double-channel trace syringe pump；3: gas flowmeter；4: quartz tube reactor；5: insulating tube；6: electric heating tube；7:
Electric heating temperature instrument；8: thermocouple；9: distribution of net；10: condenser pipe；11: liquid header；12: mixture of ice and water；13: soap bubble
Flowmeter；14: gas chromatograph.
Specific embodiment
The present invention is further illustrated with embodiment below, but the present invention is not intended to be limited thereto.
In following embodiment, the online matter of Max 300-LG type that the on-line mass spectroscopy instrument used produces for Extrel company, the U.S.
Spectrometer.
In following embodiment, the biomass catalyzing reforming catalyst used is urged for the Z409 catalytic reforming that Qilu Petrochemical is purchased
Agent.
Embodiment 1
A method of reducing catalytic reforming catalyst carbon distribution deactivation rate, comprising the following steps:
Step 1: the activation of catalytic reforming catalyst
Z409 catalytic reforming catalyst is crushed to the catalytic reforming catalyst powder that partial size is 0.18-0.25mm；Z409
Before each use of catalytic reforming catalyst, all it is with 5 hours of reduction, the temperature of reduction under the mixed airflow of hydrogen and nitrogen
500 DEG C, the Z409 catalytic reforming catalyst after being activated, wherein in the mixed airflow of hydrogen and nitrogen, by Mole percent
Than hydrogen: nitrogen=15:85.
Step 2: biomass gasifies
Product using biomass as raw material, after 700-900 DEG C of high-temperature gasification, after being gasified；
Product after gasification includes tar；
The tar is the product liquid that can not be coagulated under room temperature, also referred to as biomass coke tar.
The biomass is the biomass material of this field routine, can be agricultural wastes, forestry waste, forestry
One of processing waste, water plant and energy crop are a variety of.The biomass material that the present embodiment is selected is sawdust, gas
Changing temperature is 750 DEG C, and resulting tar is biomass coke tar；
Step 3: water vapour catforming
Hydrogen peroxide is added in Xiang Shuizhong, obtains the mixture of water and hydrogen peroxide, by after gasification product, water and hydrogen peroxide it is mixed
It closes object to be passed through in fixed bed tube furnace, carries out catalytic reforming.Wherein, hydrogen peroxide accounts for the quality percentage of the mixture of water and hydrogen peroxide
Than for 1wt.%.
Embodiment 2
A method of reducing catalytic reforming catalyst carbon distribution deactivation rate, comprising the following steps:
Step 1: the activation of catalytic reforming catalyst
Z409 catalytic reforming catalyst is crushed to the catalytic reforming catalyst powder that partial size is 0.18-0.25mm；Z409
Before each use of catalytic reforming catalyst, all it is with 5 hours of reduction, the temperature of reduction under the mixed airflow of hydrogen and nitrogen
500 DEG C, the Z409 catalytic reforming catalyst after being activated, wherein in the mixed airflow of hydrogen and nitrogen, by Mole percent
Than hydrogen: nitrogen=15:85.
Step 2: biomass gasifies
Product using biomass as raw material, after 700-900 DEG C of high-temperature gasification, after being gasified；
Product after gasification includes tar；
The tar is the product liquid that can not be coagulated under room temperature, also referred to as biomass coke tar.
The biomass is the biomass material of this field routine, can be agricultural wastes, forestry waste, forestry
One of processing waste, water plant and energy crop are a variety of.The biomass material that the present embodiment is selected is sawdust, gas
Changing temperature is 750 DEG C, and resulting tar is biomass coke tar；
Step 3: water vapour catforming
Hydrogen peroxide is added in Xiang Shuizhong, obtains the mixture of water and hydrogen peroxide, spare；Wherein, hydrogen peroxide accounts for water and hydrogen peroxide
The mass percent of mixture is 3wt.%.Product, water after gasification is passed through in fixed bed tube furnace, catalytic reforming is carried out
8min, by water switch in water be added 3wt.% hydrogen peroxide mixture be passed through in fixed bed tube furnace, allow gasification after product
Reform 8min.The mixture for being hydrated dual oxide is switched into water again, repeatedly, carries out catalytic reforming.
Experimental example 1
This experimental example improves the accurate of data to reduce fluctuation when measuring the carbon deposition rate of catalytic reforming catalyst
Property, using a kind of device for measuring catalytic reforming catalyst carbon distribution deactivation rate, structural schematic diagram is shown in Fig. 1, comprising: gas supplies
Answer system, feed system, reaction system, product analysis system, electric-heating control system；
The gas supply system includes nitrogen cylinder 1 and gas flowmeter 3；
The feed system includes double-channel trace syringe pump 2；In the double-channel trace syringe pump 2, first is logical
Biomass coke tar is injected in road, the mixture of injection water and hydrogen peroxide in second channel；Wherein, the quality of hydrogen peroxide accounts for water and double
The mass percent of oxygen aqueous mixtures is 3%.
The reaction system includes quartz tube reactor 4, distribution of net 9, insulating tube 5, condenser pipe 10, liquid header
11；
The product analysis system includes soap bubble flowmeter 13 and gas chromatograph 14；
The electric-heating control system includes electric heating tube 6 and electric heating temperature instrument 7；
The nitrogen cylinder 1 is connected to by gas flowmeter 3 with 4 feed inlet of quartz tube reactor；Double-channel trace note
The channel outlet for penetrating pump 2 is connected to by pipeline with 4 feed inlet of quartz tube reactor；
Distribution of net 9 is provided in the middle part of the pipeline of quartz tube reactor 4,4 surrounding of quartz tube reactor is provided with insulating tube
5,4 discharge port of quartz tube reactor is sequentially connected condenser pipe 10 and liquid header 11, and the gas vent of liquid header 11 is logical
It crosses triple valve and is separately connected soap bubble flowmeter 13 and gas chromatograph 14；
Electric heating tube 6 is provided between insulating tube 5 and quartz tube reactor 4, electric heating tube 6 and electric heating temperature instrument 7 connect
It connects；Electric heating temperature instrument 7 connects thermocouple 8, and thermocouple 8 is arranged inside quartz tube reactor 4, is used for real-time monitoring quartz ampoule
Temperature in reactor 4.
The liquid header 11 is arranged in mixture of ice and water.
The present embodiment, with the H in water containing 1%2O2, the device of use, structural schematic diagram is shown in Fig. 1.
A method of measurement catalytic reforming catalyst carbon distribution deactivation rate, using above-mentioned apparatus, comprising the following steps:
(1) Z409 catalytic reforming catalyst is crushed to the catalytic reforming catalyst powder that partial size is 0.18-0.25mm；
Before each use of Z409 catalytic reforming catalyst, all with 5 hours of reduction, the temperature of reduction under the mixed airflow of hydrogen and nitrogen
Degree is 500 DEG C, the Z409 catalytic reforming catalyst after activate, wherein in the mixed airflow of hydrogen and nitrogen, presses moles hundred
Divide ratio, hydrogen: nitrogen=15:85.
It (2) is that 0.18-0.25mmZ409 catalyst is packed into the distribution of net 9 at 4 middle part of quartz tube reactor by partial size, filling
Height is 6cm.Then reaction unit is connected intact.Then with the high pure nitrogen of 2L/min, reaction system is purged into 30min,
Reaction system is become into inert atmosphere.
(3) electric heating temperature instrument 7 is set as 900 DEG C of reaction temperature after, makes quartz tube reactor 4 in electric heating tube 6
Under the action of start to warm up.
It (4) is 0.3L/min by the flow set of nitrogen stream meter 3 after quartz tube reactor 6 reaches set temperature.
(5) flow of the tar of double-channel trace syringe pump 2 and water is respectively set as 10mL/h (tar) and 20mL/h
(mixture comprising deionized water and hydrogen peroxide that mass percent is 1% hydrogen peroxide), starts to feed later.
Biomass material selected by the present embodiment is sawdust, and gasification temperature is 750 DEG C, and resulting tar is biomass char
Oil ingredient is as shown in table 1.
The chemical composition of 1 biomass coke tar of table
| Number | Chemical composition | Percentage composition/wt.% | Number | Chemical composition | Percentage composition/wt.% |
| 1 | Toluene | 44.29 | 2 | Styrene | 27.83 |
| 3 | Ethylbenzene | 12.35 | 4 | Paraxylene | 9.60 |
| 5 | Naphthalene | 1.78 | 6 | Indenes | 1.69 |
| 7 | Acenaphthene | 0.78 | 8 | Phenol | 0.65 |
| 9 | Paracresol | 0.34 | 10 | 1- methyl naphthalene | 0.27 |
| 11 | Luxuriant and rich with fragrance anthracene | 0.15 | 12 | 2- methyl naphthalene | 0.13 |
| 13 | O-cresol | 0.08 | 14 | Fluorenes | 0.06 |
| 15 | Anthracene | It is micro | 16 | Anthracene | It is micro |
(6) after quartz tube reactor catalytic reforming, entire reaction temperature is 900 DEG C, and the entire reaction time is 12 small
When, reaction product is after condensing tube condensation, and liquid product collection is in liquid header；The temperature of liquid header is 0 DEG C；
(7) non-condensable gas in liquid header flows separately through soap bubble flowmeter and gas chromatograph, soap bubble flowmeter
The flow of non-condensable gas is measured, the ingredient of chromatographic non-condensable gas determines that non-condensable gas product forms.
(8) after reaction, reactor is down to room temperature in the nitrogen of 3L/min, Z409 catalytic reforming catalyst is removed
Reactor, carbon deposition rate are measured using temperature programmed oxidation, the specific steps are as follows:
Catalytic reforming catalyst after reaction is placed in another quartz tube reactor, is passed through into quartz tube reactor
The nitrogen oxygen mixture of 60mL/h, wherein in nitrogen oxygen mixture, O2Account for N2Molar percentage be 15%, by quartz tube reactor with
The rate of 10 DEG C/min is raised to 900 DEG C from room temperature, the tail gas of production is passed through in on-line mass spectroscopy instrument, carries out on-line continuous analysis,
Obtain CO production quantity m1、CO2Production quantity m2, the carbon deposition rate v of catalytic reforming catalyst is calculated according to the following formula；
Carbon source is the mass M of C are as follows: M=(m1/28+m2/44)×12；
In formula, M is the quality of carbon, unit g, m1For CO production quantity, unit g, m2For CO2Production quantity, unit g.
According to the quality of carbon, the carbon deposition rate v of catalytic reforming catalyst is calculated are as follows:
V=M ÷ m ÷ t；
Wherein, v is the carbon deposition rate of catalytic reforming catalyst, unit g/g/min；M is the quality of carbon, unit g, m
For the quality of catalytic reforming catalyst, unit g, t are catalytic reforming time, unit min.
It tests by analysis, the content of hydrogen is 58.45% in non-condensable gas after reaction, hydrogen yield 97.82%,
The carbon deposition rate of catalyst is 1.2 × 10-6g/g catalyst/min。
Experimental example 2
A kind of device measuring catalytic reforming catalyst carbon distribution deactivation rate, with experimental example 1.
A method of measurement catalytic reforming catalyst carbon distribution deactivation rate, using above-mentioned apparatus, comprising the following steps:
(1) catalytic reforming catalyst is fitted into the distribution of net 9 in quartz tube reactor 4；
(2) nitrogen cylinder 1 is opened, nitrogen gas flow 1-3L/min, purging to quartz is controlled by gas flowmeter 3
Environment fades to inert atmosphere in pipe reactor 4；
(3) electric heating temperature instrument 7 being set as reaction temperature, electric heating tube 6 heats quartz tube reactor 4, when
After the temperature of quartz tube reactor 4 reaches reaction temperature, nitrogen gas flow 0.2-0.5L/ is adjusted by gas flowmeter 3
min；
(4) it is anti-to be passed through quartz ampoule after adjusting according to reaction flowrate proportioning for the tar and water of double-channel trace syringe pump 2
It answers in device 4, is reacted at 850 DEG C, obtain reaction product；Wherein, in molar ratio, water: carbon=(2-3): 1 in tar；Water
In, the quality of hydrogen peroxide is the 3% of water and hydrogen peroxide mixture quality；
(5) reaction product is after the condensation of condenser pipe 10, and liquid product collection is in liquid header 11, liquid header
11 temperature are 0 DEG C；
(6) non-condensable gas in liquid header 11 flows separately through soap bubble flowmeter 13 and gas chromatograph 14, soap bubble
Flowmeter 13 measures the flow of the gas prepared after catalytic reforming, the gas prepared after the measurement measurement catalytic reforming of gas chromatograph 14
The ingredient of body determines that product forms；
(7) using the nitrogen in nitrogen cylinder that the device for measuring catalytic reforming catalyst carbon distribution deactivation rate is cooling, it will
Catalytic reforming catalyst after being distributed line response carries out the measurement of catalytic reforming catalyst carbon distribution, is carried out using temperature programmed oxidation
Analysis, the specific steps are as follows:
Catalytic reforming catalyst after reaction is placed in another quartz tube reactor, is passed through into quartz tube reactor
The nitrogen oxygen mixture of 60mL/h, wherein in nitrogen oxygen mixture, O2Account for N2Molar percentage be 15%, by quartz tube reactor with
The rate of 10 DEG C/min is raised to 900 DEG C from room temperature, the tail gas of production is passed through in on-line mass spectroscopy instrument, carries out on-line continuous analysis,
According to CO, CO2Production quantity calculates the carbon deposition rate of catalytic reforming catalyst by the calculation method in experimental example 1.
In the present embodiment, by calculating, the carbon deposition rate of catalytic reforming catalyst is 1.5 × 10-6g/g catalyst/
min.The content of hydrogen is 56.78% in non-condensable gas after reaction, hydrogen yield 95.37%.
Comparative example
A kind of device measuring catalytic reforming catalyst carbon distribution deactivation rate, with experimental example 2.
A method of measurement catalytic reforming catalyst carbon distribution deactivation rate, with experimental example 2, the difference is that: bilateral
In the water of road micro-injection pump, hydrogen peroxide is not added, it is measured, measurement result are as follows: the product of catalytic reforming catalyst
Carbon rate is 2.3 × 10-6g/g catalyst/min.The content of hydrogen is 56.84% in non-condensable gas after reaction, and hydrogen produces
Rate is 94.15%.
By comparing above, the carbon deposition rate reduction by 34.78% of catalytic reforming catalyst after hydrogen peroxide, hydrogen is added in discovery
Concentration is basically unchanged, and hydrogen yield slightly increased.
Claims (10)
1. a kind of method for reducing catalytic reforming catalyst carbon distribution deactivation rate, which is characterized in that this method is to urge in vapor
Change in reforming process, in catalytic reforming tar, adds hydrogen peroxide in catalytic reforming reaction object vapor, wherein hydrogen peroxide
Additional amount account for the mass percent of vapor and dioxygen aqueous mixtures are as follows: 0%-10% is added when for 0% for interval
Hydrogen peroxide.
2. it is according to claim 1 reduce catalytic reforming catalyst carbon distribution deactivation rate method, which is characterized in that when for
Interval addition hydrogen peroxide, intermittent time≤10min.
3. the method according to claim 1 for reducing catalytic reforming catalyst carbon distribution deactivation rate, which is characterized in that water steams
During gas catalytic reforming tar, catalytic reforming temperature is 650-950 DEG C；In molar ratio, vapor: carbon in tar=
(2-3): 1.
4. the method according to claim 1 for reducing catalytic reforming catalyst carbon distribution deactivation rate, which is characterized in that described
Tar, be the by-product of biomass gasifying hydrogen making, the by-product of biomass cracking hydrogen manufacturing, hydrogen production from coal gasification by-product, coal
One of by-product of cracking hydrogen production.
5. the method according to claim 4 for reducing catalytic reforming catalyst carbon distribution deactivation rate, which is characterized in that described
Biomass gasifying hydrogen making by-product, be that the raw material of biomass passes through 700-900 DEG C of high-temperature gasification, obtained room temperature can not coagulate
Product liquid is tar.
6. the method according to claim 5 for reducing catalytic reforming catalyst carbon distribution deactivation rate, which is characterized in that described
Biomass raw material select agricultural wastes, forestry waste, forestry processing Litter, in water plant and energy crop
It is one or more of.
7. the method according to claim 1 for reducing catalytic reforming catalyst carbon distribution deactivation rate, which is characterized in that described
Water vapour catforming during, the catalytic reforming catalyst used is nickel-base catalyst.
8. the application of the method for catalytic reforming catalyst carbon distribution deactivation rate is reduced described in claim 1~7 any one,
It is characterized in that, this method is for the catalytic reforming process of biomass gasifying hydrogen making, the catalytic reforming mistake of biomass through pyrolysis hydrogen manufacturing
Journey, the catalytic reforming process of hydrogen production from coal gasification, the catalytic reforming process of coal thermal cracking hydrogen manufacturing, gas water steam catalytic are reformed
One of journey process.
9. the application of the method according to claim 8 for reducing catalytic reforming catalyst carbon distribution deactivation rate, feature exist
In the catalytic reforming process of the biomass gasifying hydrogen making includes the steps that are as follows:
(1) catalytic reforming catalyst is filled in fixed bed tube furnace；
(2) fixed bed tube furnace is purged using nitrogen, so that being inert atmosphere in fixed bed tube furnace；
(3) fixed bed tube furnace is warming up to 650-950 DEG C of reaction temperature, after temperature reaches reaction temperature and stablizes, by nitrogen
Throughput is adjusted to 0m/s；
(4) product after the mixture and gasification of biomass of mixed hydrogen peroxide according to the ratio and water is passed through fixed bed pipe
In formula furnace, catalytic reforming is carried out；Wherein, in the mixture of hydrogen peroxide and water, hydrogen peroxide accounts for the quality of water and dioxygen aqueous mixtures
Percentage is 0-10%, and when for 0%, interval is passed through the mass percent that hydrogen peroxide accounts for and is greater than 0% pair less than or equal to 10%
The mixture of oxygen water and water, wherein in molar ratio, water: carbon=(2-3): 1 in tar.
10. the application of the method according to claim 9 for reducing catalytic reforming catalyst carbon distribution deactivation rate, feature exist
In in the step (2), the flow and purge time of nitrogen are according to the specification and catalytic reforming catalyst of fixed bed tube furnace
Filling height determine, flow velocity 10-25m/s.
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