CN100462299C - Method for producing synthetic gas by reforming by-product glycerin vapor of biological diesel production - Google Patents
Method for producing synthetic gas by reforming by-product glycerin vapor of biological diesel production Download PDFInfo
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- CN100462299C CN100462299C CNB2007100573111A CN200710057311A CN100462299C CN 100462299 C CN100462299 C CN 100462299C CN B2007100573111 A CNB2007100573111 A CN B2007100573111A CN 200710057311 A CN200710057311 A CN 200710057311A CN 100462299 C CN100462299 C CN 100462299C
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- steam
- reforming
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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
- Y02P20/00—Technologies relating to chemical industry
- 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
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Abstract
The invention discloses a preparing method of synthetic gas through reforming the by-product glycerin steam of biological diesel in the preparing technology of synthetic gas, which comprises the following steps: filling Ni/ZrO2 or Ni/CeO2 or Ni/CeO2-ZrO2 activator into reactor; setting the content of nickel at 10%-15%; adopting hydrogen gas and nitrogen gaseous mixture; proceeding reducing pre-treatment for the activator; leading glycerin water solution steam into the reactor with air speed at 5000-20000h-1 and ratio of water and carbon at 1:1-5:1; steam-reforming under normal pressure and with temperature at 300-600 deg. c; preparing the product. This invention possesses the advantages of simple craft course, low cost and wide prospect, which is fit for the requirement of green chemistry.
Description
Technical field
The present invention relates to a kind of by-product glycerin and carry out the method that steam reformation prepares synthetic gas, belong to the synthesis gas preparation technology with the production biofuel.
Background technology
Biofuel is a kind of mono alkyl ester of longer chain fatty acid, can make by renewable resourcess such as animal-plant oil and methyl alcohol transesterify, comparing with mineral diesel, have during use that air pollutant emission is few, oilness good, biological degradation waits advantage fully, is the New-type fuel that various countries competitively develop
[1]Can produce glycerin by-products in the ester-interchange method production biofuel process, output generally accounts for about yield of biodiesel 10wt%.The development and use of glycerine byproduct, one side can effectively reduce the production cost of biofuel
[2]Thereby, promote promoting the use of of biofuel; Can fill up the demand vacancy of market on the other hand, effectively reduce the market value of glycerine glycerine.
As a kind of polyhydroxy-alcohol, when glycerine directly carries out thermo-cracking, can obtain H in theory
2/ CO is 1.33 synthetic gas.If adopt the method for steam reformation, then can further regulate the H in the product gas
2/ CO, thus satisfy different synthetic needs.The raw glycerine product that employing steam reformation technology can also directly be utilized biodiesel byproduct is as raw material, and the heat that its vaporization is carried out reaction needed is equal to the heat that its separation is obtained the pure glycerin product needed
[3]If to carry out heat integrated with the Fischer-Tropsch synthesis process of follow-up heat release, then this technology can further effectively reduce energy consumption.In addition, adopt the glycerine of biodiesel byproduct to prepare synthetic gas, in its product gas not sulfur-bearing and halogen etc. catalyzer is poisoned bigger impurity, need not corresponding gas purification process, can effectively reduce production costs.H when the gained synthetic gas
2/ CO is 1～2 o'clock, carry out that Fischer-Tropsch is synthetic can produce gasoline or diesel oil, thereby the purpose for preparing oil product fuel with animal-plant oil on the source is consistent, can also further realize the technical scale production of technology under the help of catalyzer, thereby reaches the maximization of aims of systems product.In the recent period, Dumesic etc.
[3,4]Adopt the Pt catalyzer to carry out the experiment of glycerin vapor preparing synthetic gas by reforming.At normal pressure, 225～377 ℃ of temperature of reaction under the condition of glycerol content 30wt%, adopt oxide carriers such as MgO, can produce H
2/ CO is at 1.3～1.7 synthetic gas.Along with the continuous expansion of yield of biodiesel, the output of its glycerin by-products also increases sharply, but the use of noble metal catalyst will be unfavorable for the development and use of its mass-producing.
The main reference document:
[1] Min Enze, Tang Zhong, Du Zexue etc., the discussion of development China biofuel industry, Chinese engineering science, 2005,7 (4), 1-4,35
[2]M.J.Haas，A.J.McAloon，W.C.Yee，et?al.A?process?model?to?estimate?biodiesel?production?costs.Bioresource?Technology.2006，97，671-678
[3]R.R.Soares，D.A.Simonetti，and?J.A.Dumesic.Glycerol?as?a?Source?for?Fuels?and?Chemicals?byLow-Temperature?Catalytic?Processing，Angewandte?Chemie-International?Edition.2006，45，3982-3985
[4]D.A.Simonetti，E.L.Kunkes，J.A.Dumesic，Gas-phase?conversion?of?glycerol?to?synthesis?gas?overcarbon-supported?platinum?and?platinum-rhenium?catalysts，Journal?of?Catalysis，2007，247，298-306
Summary of the invention
The object of the present invention is to provide a kind of is that raw material carries out the method that steam reformation prepares synthetic gas to produce biological diesel oil byproduct glycerin, and it is metal catalyst that this method adopts nickel, and it is renewable to have a raw material, characteristics such as the catalyzer cost is low, catalytic activity height.
The objective of the invention is to be achieved through the following technical solutions.A kind ofly prepare the method for synthetic gas, it is characterized in that comprising following process to produce the biological diesel oil byproduct glycerin steam reformation:
At first in reactor, load Ni/ZrO
2Or Ni/CeO
2Or Ni/CeO
2-ZrO
2Catalyzer, the mass content of catalyst activity component nickel is 10%～15%, adopts the hydrogen and the nitrogen mixture of hydrogen volume content 5%, with flow 100ml/min, at 400～600 ℃ of following prereduction catalyzer 1.5～2h, then to reactor with air speed 5000～20000h
-1Feed water molecules and carbon atom number ratio, promptly steam/hydrocarbons ratio is the aqueous glycerin solution steam of 1:1～5:1, at normal pressure, carries out steam reforming reaction under 300～600 ℃ the condition, obtains H
2The syngas product of/CO in 1.1～2.5 scopes.
The steam/hydrocarbons ratio of above-mentioned aqueous glycerin solution steam is 2～4, and temperature of reaction is 400～500 ℃, and gas space velocity is 5000～10000h
-1
Advantage of the present invention, the catalyst preparation process that is adopted is simple, and is easy to operate, and the catalyzer that makes has the catalytic activity height, and selectivity is good, and stability is strong; Raw material adopts the raw glycerine by product of production biofuel, meets the Green Chemistry requirement; The technological process of preparation synthetic gas is simple to operate, with low cost, is used to develop its derived product and has a extensive future.
Embodiment
Embodiment 1:
The preparation of nickel catalyst
Preparation process: (1) compound concentration is the zirconyl chloride solution of 1.0mol/L; (2) compound concentration is the cerous nitrate solution of 1.0mol/L; (3) measure cerous nitrate solution and zirconyl chloride solution according to Ce/Zr=1/1, preparation Ce
3+, Zr
4+Total ion concentration is the mixing solutions of 1.0mol/L; To above-mentioned three kinds of solution, be respectively precipitation agent with ammoniacal liquor, and drip add and precipitates and constantly stir, the control pH value of solution is 9.5～10.5.Precipitation is the aging 12h in back fully, is 7 and detects less than Cl with Silver Nitrate to pH with deionized water wash
-1, 120 ℃ of dry 12h, 600～800 ℃ of roasting 2～5h obtain CeO respectively
2, ZrO
2And CeO
2-ZrO
2Powder, specific surface area 20～80m
2/ g.By the Ni mass content is 10%～15% to take by weighing three parts of nickelous nitrates, being mixed with concentration respectively is three parts of solution of 0.2mol/L, take by weighing to adopt the oxide powder that said process makes and join respectively in the nickel nitrate solution for preparing and flood, remove aqueous solvent through 70～80 ℃ of following rotary evaporations, 120 ℃ of vacuum-drying 12h, 600～800 ℃ of roasting 2～4h obtain the Ni/CeO of Ni mass content 10%～15% respectively
2, Ni/ZrO
2And Ni/CeO
2-ZrO
2Catalyzer, specific surface area 50～100m
2/ g.
With 10wt% Ni/ZrO
2The catalyzer 400mg internal diameter of packing into is in the reactor of 6mm, adopts the H of hydrogen volume content 5%
2-N
2Gas mixture 100mL/min is at 400 ℃ of following prereduction 2h, at N
2Protection drops to 300 ℃, is 10000h with the air speed to reactor
-1, the feeding steam/hydrocarbons ratio is that the aqueous glycerin solution steam of 2:1 reacts.Reaction result is as follows: glycerol conversion yield 95%, the product mole consists of: H
2: 45.6%, CO:35.6%, CO
2: CH 17.0%,
4: 1.8%, H
2/ CO=1.28.
Embodiment 2:
The 15wt%Ni/CeO that employing makes by embodiment 1 method
2Catalyzer 200mg, the H of employing hydrogen volume content 5%
2-N
2Gas mixture is set reaction velocity 15000h at 500 ℃ of following prereduction 2h
-1, aqueous glycerin solution steam water carbon ratio 3:1,500 ℃ of temperature of reaction, other experiment condition is with embodiment 1.Reaction result is as follows: glycerol conversion yield 98%, the reaction product mole is formed: H
2: 56.8%, CO:31.9%, CO
2: CH 9.8%,
4: 1.5%, H
2/ CO=1.78.
Embodiment 3:
The 10wt%Ni/CeO that employing makes by embodiment 1 method
2-ZrO
2Catalyzer is set reaction velocity 5000h
-1, aqueous glycerin solution steam water carbon ratio 4:1,500 ℃ of temperature of reaction, the reduction of catalyzer and other experiment condition are with embodiment 2.Reaction result is as follows: glycerol conversion yield 100%, the reaction product mole is formed: H
2: 62.7%, CO:25.3%, CO
2: CH 10.7%,
4: 1.3%, H
2/ CO=2.48.
Embodiment 4:
The 15wt%Ni/CeO that employing makes by embodiment 1 method
2-ZrO
2Catalyzer 200mg, the H of employing hydrogen volume content 5%
2-N
2Gas mixture is set aqueous glycerin solution steam water carbon ratio 5:1 at 600 ℃ of following prereduction 1.5h, 600 ℃ of temperature of reaction, and other experiment condition is with embodiment 1.Reaction result is as follows: glycerol conversion yield 100%, the reaction product mole is formed: H
2: 69.2%, CO:22.5%, CO
2: CH 7.8%,
4: 0.5%, H
2/ CO=3.08.
Embodiment 5:
The 10wt%Ni/CeO that employing makes by embodiment 1 method
2Catalyzer is set reaction velocity 5000h
-1, aqueous glycerin solution steam water carbon ratio 1:1,400 ℃ of temperature of reaction, the reduction of catalyzer and other experiment condition are with embodiment 2.Reaction result is as follows: glycerol conversion yield 96%, the product mole consists of: H
2: 43.6%, CO:40.4%, CO
2: CH 13.9%,
4: 2.1%, H
2/ CO=1.08.
Embodiment 6:
The Ni/ZrO of the 15wt% that employing makes by embodiment 1 method
2Catalyzer 200mg sets reaction velocity 20000h
-1, aqueous glycerin solution steam water carbon ratio 3:1,500 ℃ of temperature of reaction, the reduction of catalyzer and other experiment condition are with embodiment 2.Reaction result is as follows: glycerol conversion yield 100%, the reaction product mole is formed: H
2: 59.6%, CO:29.4%, CO
2: CH 9.6%,
4: 1.4%, H
2/ CO=2.03.
Claims (2)
1. the method with the reforming by-product glycerin vapor preparing synthetic gas of production biofuel is characterized in that comprising following process: at first load Ni/ZrO in reactor
2Or Ni/CeO
2Or Ni/CeO
2-ZrO
2Catalyzer, the mass content of this catalyst activity component nickel is 10%～15%, and adopting hydrogen volume content is 5% the hydrogen and the gas mixture of nitrogen, is 100mL/min with the flow, at 400～600 ℃ of following prereduction catalyzer 1.5～2h, then to reactor with air speed 5000～20000h
-1Feed water molecules and carbon atom number ratio, promptly steam/hydrocarbons ratio is the aqueous glycerin solution steam of 1:1～5:1, at normal pressure, carries out steam reforming reaction under 300～600 ℃ the condition, obtains H
2The syngas product of/CO mol ratio in 1.1～2.5 scopes.
2. by the method for the described reforming by-product glycerin vapor preparing synthetic gas with the production biofuel of claim 1, it is characterized in that: the steam/hydrocarbons ratio of aqueous glycerin solution steam is 2～4, and air speed is 5000～10000h
-1, temperature of reaction is 400～500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100573111A CN100462299C (en) | 2007-05-10 | 2007-05-10 | Method for producing synthetic gas by reforming by-product glycerin vapor of biological diesel production |
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|---|---|---|---|
| CNB2007100573111A CN100462299C (en) | 2007-05-10 | 2007-05-10 | Method for producing synthetic gas by reforming by-product glycerin vapor of biological diesel production |
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| CN100462299C true CN100462299C (en) | 2009-02-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018026388A1 (en) * | 2016-08-05 | 2018-02-08 | Greyrock Energy, Inc. | Catalysts, related methods and reaction products |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2103567A1 (en) * | 2008-03-10 | 2009-09-23 | Gelato Corporation N.V. | Process for the preparation of synthesis gas, II |
| CN102718184B (en) * | 2011-03-29 | 2015-04-08 | 鞍钢股份有限公司 | System for producing hydrogen from recovered waste glycerin by using heating-furnace flue gas and recovery method thereof |
| RU2553457C1 (en) * | 2013-11-08 | 2015-06-20 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Catalyst of steam conversion of hydrocarbons and method of obtaining thereof |
| CN114249299B (en) * | 2021-11-09 | 2023-06-23 | 浙江思欣通氢能科技有限公司 | Pretreatment method for methane-rich gas plasma multi-reforming reaction catalyst |
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| CN1240757A (en) * | 1999-08-02 | 2000-01-12 | 石油大学(北京) | Process for preparing synthetic gas by two-stage catalytic oxidization of natural gas |
| CN1468800A (en) * | 2003-06-20 | 2004-01-21 | 中国科学院广州能源研究所 | Autothermal catalytic marsh gas reforming process of preparing synthetic gas |
| JP2004167414A (en) * | 2002-11-21 | 2004-06-17 | Ishikawajima Harima Heavy Ind Co Ltd | Catalyst for synthetic gas generation and method for producing the same |
| CN1656013A (en) * | 2001-11-29 | 2005-08-17 | 威斯康星旧生研究基金会 | Low-temperature hydrogen production from oxygenated hydrocarbons |
| CN1706743A (en) * | 2004-06-09 | 2005-12-14 | 华东理工大学 | Process of preparing hydrogen with biomass fast cracking oil |
-
2007
- 2007-05-10 CN CNB2007100573111A patent/CN100462299C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240757A (en) * | 1999-08-02 | 2000-01-12 | 石油大学(北京) | Process for preparing synthetic gas by two-stage catalytic oxidization of natural gas |
| CN1656013A (en) * | 2001-11-29 | 2005-08-17 | 威斯康星旧生研究基金会 | Low-temperature hydrogen production from oxygenated hydrocarbons |
| JP2004167414A (en) * | 2002-11-21 | 2004-06-17 | Ishikawajima Harima Heavy Ind Co Ltd | Catalyst for synthetic gas generation and method for producing the same |
| CN1468800A (en) * | 2003-06-20 | 2004-01-21 | 中国科学院广州能源研究所 | Autothermal catalytic marsh gas reforming process of preparing synthetic gas |
| CN1706743A (en) * | 2004-06-09 | 2005-12-14 | 华东理工大学 | Process of preparing hydrogen with biomass fast cracking oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018026388A1 (en) * | 2016-08-05 | 2018-02-08 | Greyrock Energy, Inc. | Catalysts, related methods and reaction products |
| US10260005B2 (en) | 2016-08-05 | 2019-04-16 | Greyrock Technology LLC | Catalysts, related methods and reaction products |
| US11332674B2 (en) | 2016-08-05 | 2022-05-17 | Greyrock Technology, Llc | Catalysts, related methods and reaction products |
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| CN101062762A (en) | 2007-10-31 |
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