CN108726833A - A kind of municipal sludge situ catalytic vaporizing system for high-purity hydrogen new process - Google Patents
A kind of municipal sludge situ catalytic vaporizing system for high-purity hydrogen new process Download PDFInfo
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- CN108726833A CN108726833A CN201810565769.6A CN201810565769A CN108726833A CN 108726833 A CN108726833 A CN 108726833A CN 201810565769 A CN201810565769 A CN 201810565769A CN 108726833 A CN108726833 A CN 108726833A
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- Prior art keywords
- gasification
- municipal sludge
- hydrogen
- sludge
- hydro
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
Abstract
The invention discloses a kind of municipal sludge situ catalytic vaporizing systems for the new process of high-purity hydrogen, and the tar by-product that can effectively generate during catalytic degradation sludge gasification simultaneously improves hydrogen volume score in gasification burning.Specific method is：1) by sludge and six water nickel nitrate solution mixings, pretreatment is carbonized by hydro-thermal and prepares hydro-thermal charcoal；2) using hydro-thermal charcoal as raw material, with the egg shell of calcining for natural CO2Capturing agent carries out high-temperature vapor and gasifies altogether；3) hydrogen-rich gasification burning can be obtained after gasification aerogenesis being purified, dried.Municipal sludge of the present invention " autoreduction " nano-metal particle in situ couples original position CO2The technology path of hydrogen manufacturing is strengthened in capture, and the In-stiu catalysis reaction of tar can occur on nano nickel activated centre, and promotes the forward reaction rate of water-gas shift reaction, to realize prepared by the cleaning low consumption of low tar, hydrogen-rich combustion gas.
Description
Technical field
The present invention relates to a kind of municipal sludge " autoreduction " nano particles in situ to couple original position CO2Hydrogen conversion is strengthened in capture
Technology path, realize the gasification conversion of the low tar of municipal sludge, high hydrogen volume score, municipal sludge can be effectively improved
Gasification efficiency and fuel gases calorific value.
Technical background
As China's urban sewage treatment process is continuously improved, municipal sludge yield sharply increases.Conventional process mode (is filled out
Bury, burn) secondary pollution easily is caused to soil, atmospheric environment.Pyrolytic gasification technology because with energy regenerating, reducing sludge volume without
The features such as evilization, short disposition period, is with wide development potentiality.However, traditional gasification technology need that raw material is dried it is pre-
Processing, municipal sludge initial aqueous rate are general>80%, dehydration pre-process cost is higher, thus limits the technology to municipal dirty
The industrially scalable of mud is handled.On the other hand, sludge traditional gasification process inevitably generates the by-products such as tar, significantly drops
Low gasification efficiency, and influence gasification synthesis gas quality.The present invention develops a kind of municipal sludge situ catalytic gasification hydrogen-producing
New process, which is not necessarily to carry out dehydration pre-process to municipal sludge, while passing through original position " autoreduction " nano-metal particle coupling
Close original position CO2The technology path of capture can convert municipal sludge to hydrogen-rich gasification synthesis gas.By the research and development of the new process,
The quick volume reduction of municipal sludge can be promoted to be reduced, reduce hydrogen manufacturing production cost and reduce traditional fossil energy consumption, meeting can not
The energy development trend that regenerated carbon-based resources are converted to reproducible biomass resource.
Invention content
The purpose of the present invention is be directed to existing convert high-moisture percentage municipal sludge to using pyrolytic gasification technology to clean combustion
The practical problems such as pretreatment of raw material is of high cost during gas, fuel gases calorific value is low, tar by-product purification cost height, in conjunction with China's mesh
The present situation that preceding municipal sludge total amount is urgently handled proposes a kind of new process of municipal sludge situ catalytic gasification hydrogen-producing.The present invention
Gasification synthesis gas tar by-products content prepared by method is low, and hydrogen volume score is high, and the process route is environmental-friendly, raw material at
This is cheap, and preparation method is simple and direct reliable.
To achieve the purpose of the present invention, the present invention provides a kind of technology path of municipal sludge situ catalytic gasification.With city
Political affairs sludge is raw material, without dry pretreatment, by primary sludge and certain density Nickelous nitrate hexahydrate by certain mass than mixed
It closes, mixture is placed in autoclave and carries out hydro-thermal charing pretreatment, after reaction separation and Extraction solid product, then
With the egg shell of calcining for natural CO2Capturing agent carries out total gasification, purification is dry using vapor as gasifying medium with solid product
Hydrogen-rich synthetic gas can be obtained after dry.Tar highest degradation rate in the gasification synthesis gas of preparation>98%, hydrogen volume score>70%.
The gasification result of the technique is by precursor concentration, hydro-thermal carbonization temperature, hydro-thermal carbonization time, CO2Capturing agent additive amount, gasification temperature
The influence of the factors such as degree.
Main advantages of the present invention are embodied in following several respects：
High-moisture percentage municipal sludge carries out hydro-thermal charcoal after being sufficiently mixed with Nickelous nitrate hexahydrate solution in autoclave
Change pretreatment, the reason is that：Nanometer is realized using the abundant electronics transfer group of hydro-thermal carbon surface in sludge hydrothermal reaction process
" autoreduction " of nickel particle, to provide active site for follow-up gasification situ catalytic degradation tar by-product.
The concentration of Nickelous nitrate hexahydrate solution is 0.1-1.0mol/L, the reason is that：Nickel ion concentration is too low, then can reduce
Hydro-thermal carbon surface active site quantity reduces catalytic degradation tar efficiency；Nickel ion concentration is excessively high, then can reduce hydro-thermal carbon surface
Active site dispersion degree, and cause nano nickle granules oversized, reduce situ catalytic reactivity.
Hydro-thermal carbonization temperature selects 180-220 DEG C, reaction time 1-2h, the reason is that：Hydrothermal temperature is relatively low or anti-
Shorter between seasonable, the reaction of sludge " autoreduction " nano particle is insufficient.Hydrothermal temperature is higher or the reaction time is longer, solid phase
Product yield reduces and energy consumption is excessively high.
Hydro-thermal is carbonized into the native egg shell of pretreated solid product and calcining as CO2Capturing agent carries out vapor
Gasification reaction altogether, the reason is that：The key component of native egg shell is CaCO3, (the CaCO after high-temperature calcination3→CaO+CO2) become
For CaO, CO can be fixed by carbonation reaction in gasification reaction2(CaO+CO2→CaCO3), to promote Water gas shift/WGS anti-
Answer (CO+H2O→CO2+H2) forward direction progress, improve H in gasification synthesis gas2Volume fraction.
Sludge gasification reaction temperature selects 700-900 DEG C, the reason is that：Gasification temperature is excessively high, is more than nano nickle granules tower
Solids are migrated along plane of crystal when graceful temperature, are spread and are recrystallized in intracell space, live so as to cause nano particle
Property phase sintering, reduce to the catalytic pyrolysis efficiency of tar by-product；Gasification temperature is too low, the reverse speed of water gas shift reaction
Rate is more than positive rate, reduces H in gasification synthesis gas2Volume fraction.
With reference to the accompanying drawings of the specification and the embodiment content that the present invention is further explained.
Description of the drawings
Fig. 1 municipal sludges " autoreduction " nano particle in situ couples original position CO2The technology path flow of hydrogen manufacturing is strengthened in capture
Schematic diagram.
Specific implementation mode
The present invention prepares low tar, hydrogen-rich gasification synthesis gas using high-moisture percentage municipal sludge.
Case study on implementation one
1. hydro-thermal charing pretreatment
1) high-moisture percentage municipal sludge and the Nickelous nitrate hexahydrate solution of 0.5mol/L concentration are pressed 1:3 ratios mix, and stir
It mixes uniformly.
2) by the mixture of high-moisture percentage municipal sludge and Nickelous nitrate hexahydrate solution merging autoclave, then will
Reactor is warming up to 220 DEG C, reaction time 1h.
3) after reaching the reaction time, reactor is cooled down rapidly by automatically recycled water, gaseous by-products is discharged, works as reaction
After device pressure reduction to normal pressure, solidliquid mixture is separated by solid-liquid separation by centrifugation, it is final to obtain solid phase target product.
2. the situ catalytic gasification reaction of municipal sludge
1) native egg shell is calcined into 2h under the conditions of 800 DEG C, solid product is as CO after collecting calcining2Capturing agent.
2) solid product after the charing pretreatment of municipal sludge hydro-thermal and egg shell product merging gasification furnace after calcining are waited for instead
It answers area, seals after gasification system with N2It purges gasification reactor system and maintains inert atmosphere.
3) high-temperature vapor is prepared by steam evaporator and is used as gasification reaction medium, wherein steam temperature is 190
℃。
4) high-temperature vapor is passed through in gasification reactor, carries out high-temperature vapor gasification, wherein gasification reaction temperature is
700℃。
5) it is dried after the thick combustion gas of steam gasification reaction gained being carried out purification tar removing, you can gasification synthesis gas is obtained,
The gasification synthesis gas of preparation is according to national standard GB/T 10410-2008 (artificial coal gas and liquefied petroleum gas major constituents gas-chromatography
Analytic approach) standard or method be detected, testing result such as table 1.
Case study on implementation two
In addition to using high-moisture percentage municipal sludge as raw material, using the native egg shell of calcining as CO2Capturing agent；
In addition to six nitric hydrates of step 1) high-moisture percentage municipal sludge and 0.1mol/L concentration in hydro-thermal charing pretreatment
Nickel solution presses 1:3 ratios mix；Step 2) hydro-thermal carbonization reaction temperature is 200 DEG C, and processing time is remaining and reality except 1.5h
It is identical to apply case one.
In situ catalytic gasification reaction other than step 4) steam gasification temperature is 800 DEG C, remaining and case study on implementation
One is identical.
Gasifying, thick gas-purification processing is identical as case study on implementation one, and the gasification synthesis gas of preparation is according to national standard GB/T
10410-2008 (artificial coal gas and liquefied petroleum gas major constituents gas chromatography) standards or method are detected, detection
As a result such as table 1.
Case study on implementation three
In addition to using high-moisture percentage municipal sludge as raw material, using the native egg shell of calcining as CO2Capturing agent；
In addition to six nitric hydrates of step 1) high-moisture percentage municipal sludge and 1.0mol/L concentration in hydro-thermal charing pretreatment
Nickel solution presses 1:3 ratios mix；Step 2) hydro-thermal carbonization reaction temperature is 180 DEG C, and processing time is remaining and implementation except 2h
Case one is identical.
In situ catalytic gasification reaction other than step 4) steam gasification temperature is 900 DEG C, remaining and case study on implementation
One is identical.
Gasifying, thick gas-purification processing is identical as case study on implementation one, and the gasification synthesis gas of preparation is according to national standard GB/T
10410-2008 (artificial coal gas and liquefied petroleum gas major constituents gas chromatography) standards or method are detected, detection
As a result such as table 1.
1 municipal sludge situ catalytic gasification burning constituent content index of table
| Project | Case study on implementation one | Case study on implementation two | Case study on implementation three |
| H2(%) | 74 | 67 | 59 |
| CO (%) | 11 | 8 | 15 |
| CH4(%) | 6 | 5 | 7 |
| Tar yield (%) | 1.2 | 3.7 | 9.5 |
The beneficial effects are mainly as follows following aspect：
1. tar highest degradation rate in gasification synthesis gas prepared by the present invention>98%, hydrogen volume score>70%.
It is pre-processed 2. being carbonized by hydro-thermal with nitric hydrate nickel and municipal sludge in the method for the present invention, utilizes hydro-thermal carbon surface
Abundant electronics transfer group realizes " autoreduction " of nano particle, and mutually strengthens municipal sludge as catalytic activity and gasified
The situ catalytic of journey tar by-product is degraded, and gasification efficiency is improved.Meanwhile tar content is low in the obtained thick combustion gas of gasification,
Reduce the investment to clean unit equipment.
3. with native egg shell being CO in the method for the present invention2Capturing agent promotes hydrogen-rich by strengthening water gas shift reaction
Gas generates, and has not only solved the waste of eggshell waste material, but also can be obviously improved the fuel gases calorific value of municipal sludge gasification.
4. gasification synthesis gas prepared by the method for the present invention, is to pass through the energy using a large amount of sewage sludge solid waste as raw material
Change using being turned waste into wealth, secondary environmental pollution caused by conventional municipal Treatment of Sludge (such as landfill, burning) can be reduced and
The raw material sources that can be prepared as gasification synthesis gas, reduce production cost, have higher economy, environmental and social benefits.
Claims (6)
1. a kind of municipal sludge situ catalytic vaporizing system is for the new process of high-purity hydrogen, it is characterised in that：By primary sludge and one
The Nickelous nitrate hexahydrate for determining concentration is mixed by certain mass ratio, and mixture is placed in autoclave and carries out hydro-thermal charing place in advance
It manages, after reaction separation and Extraction solid product, then with the egg shell of calcining for natural CO2Capturing agent, using vapor as gas
Change medium, carries out total gasification with solid product, hydrogen-rich synthetic gas, wherein hydrogen volume score can be obtained after purge drying>70%,
And tar highest degradation rate>98%.
2. a kind of municipal sludge situ catalytic vaporizing system according to claim 1 is for the new process of high-purity hydrogen, feature
It is：High-moisture percentage municipal sludge and the Nickelous nitrate hexahydrate solution of 0.1-1.0mol/L concentration are pressed 1:3 ratios mix, with laggard
The charing pretreatment of row hydro-thermal.
3. a kind of municipal sludge situ catalytic vaporizing system according to claim 1 is for the new process of high-purity hydrogen, feature
It is：Hydro-thermal carbonization temperature selects 180-220 DEG C, reaction time 1-2h.
4. a kind of municipal sludge situ catalytic vaporizing system according to claim 1 is for the new process of high-purity hydrogen, feature
It is：It carries out being total to gasification reaction with sludge after hydrothermal pretreatment after egg shell is calcined 2h under the conditions of 800 DEG C.
5. a kind of municipal sludge situ catalytic vaporizing system according to claim 1 is for the new process of high-purity hydrogen, feature
It is：High-temperature vapor is passed through in gasification reactor, high-temperature vapor is carried out and is total to gasification reaction, wherein gasification reaction temperature is
700-900℃。
6. hydrogen volume score in the gasification synthesis gas being prepared according to claim 1-5 any one the methods>70%,
And tar highest degradation rate>98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810565769.6A CN108726833A (en) | 2018-06-04 | 2018-06-04 | A kind of municipal sludge situ catalytic vaporizing system for high-purity hydrogen new process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810565769.6A CN108726833A (en) | 2018-06-04 | 2018-06-04 | A kind of municipal sludge situ catalytic vaporizing system for high-purity hydrogen new process |
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| Publication Number | Publication Date |
|---|---|
| CN108726833A true CN108726833A (en) | 2018-11-02 |
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| CN201810565769.6A Pending CN108726833A (en) | 2018-06-04 | 2018-06-04 | A kind of municipal sludge situ catalytic vaporizing system for high-purity hydrogen new process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718761A (en) * | 2020-06-15 | 2020-09-29 | 宁夏大学 | Method for preparing synthesis gas by co-gasification of hydrothermal carbon and pulverized coal in livestock and poultry waste |
| CN112063394A (en) * | 2020-06-19 | 2020-12-11 | 中国科学院生态环境研究中心 | Method for producing hydrogen-rich synthesis gas by gasifying waste biomass |
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| US20130203144A1 (en) * | 2012-01-23 | 2013-08-08 | Anaergia Inc. | Syngas biomethanation process and anaerobic digestion system |
| CN106348561A (en) * | 2016-09-06 | 2017-01-25 | 北京化工大学 | Method of recycling impregnated sludge carbon to catalytically gasify and recycling sludge carbon for secondary conversion of tar |
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- 2018-06-04 CN CN201810565769.6A patent/CN108726833A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130203144A1 (en) * | 2012-01-23 | 2013-08-08 | Anaergia Inc. | Syngas biomethanation process and anaerobic digestion system |
| CN106348561A (en) * | 2016-09-06 | 2017-01-25 | 北京化工大学 | Method of recycling impregnated sludge carbon to catalytically gasify and recycling sludge carbon for secondary conversion of tar |
Non-Patent Citations (1)
| Title |
|---|
| CHAO GAI ET AL.: "Hydrochar-Supported, in Situ-Generated Nickel Nanoparticles for Sorption-Enhanced Catalytic Gasification of Sewage Sludge", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718761A (en) * | 2020-06-15 | 2020-09-29 | 宁夏大学 | Method for preparing synthesis gas by co-gasification of hydrothermal carbon and pulverized coal in livestock and poultry waste |
| CN112063394A (en) * | 2020-06-19 | 2020-12-11 | 中国科学院生态环境研究中心 | Method for producing hydrogen-rich synthesis gas by gasifying waste biomass |
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Application publication date: 20181102 |