CN106540730A - A kind of natural gas catalyst manufactured by coal and preparation method thereof - Google Patents
A kind of natural gas catalyst manufactured by coal and preparation method thereof Download PDFInfo
- Publication number
- CN106540730A CN106540730A CN201510587811.0A CN201510587811A CN106540730A CN 106540730 A CN106540730 A CN 106540730A CN 201510587811 A CN201510587811 A CN 201510587811A CN 106540730 A CN106540730 A CN 106540730A
- Authority
- CN
- China
- Prior art keywords
- coal
- catalyst
- sill
- preparation
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to technical field of catalytic coal gasification catalysts, there is provided a kind of method that alkali metal salt is prepared as efficient catalytic coal gasifaction catalyst and application thereof.Presoma of the catalyst with alkali metal salt as catalyst, method using surfactant is added, using the hydrophilic-hydrophobic construction featuress of surface active agent composition itself, improve the wettability of coal particle surface, effective metal component is uniformly supported on coal base by traditional infusion process, active component is disperseed with atom level.Using the catalyst prepared by the present invention in the fixed bed reactors of catalytic coal gasifaction preparing natural gas, it is not only able to effectively improve the conversion ratio that coal is changed into gas-phase product, and it is capable of the composition of modulation coal gas, improves the content of methane, drastically increases the utilization rate of coal.
Description
Technical field
The present invention relates to a kind of catalyst and its production and use, more particularly to a kind of catalyst for catalytic coal gasifaction and its production and use.
Background technology
The energy resource structure of China is characterized in that many gas of coal are few, development of the coal to Chinese national economy plays an important role, but with expanding economy and the raising of living standards of the people, coal is directly as fuel, not only efficiency is low, and the gas for discharging increased PM2.5 contents in air, cause environment to be compromised.Using Coal Gasification Technology, a kind of important channel that gaseous fuel is that coal clean and effective is utilized is converted coal into.Coal is changed into into synthesis gas using Coal Gasification Technology, various important chemical products such as synthesis gas production ammonia, methanol are recycled.The Coal Gasification Technology of industrialized production is the Coal Gasification Technology without catalyst.Only when gasification temperature is 1100 ~ 1700
DEG C when, gasification reaction speed just can reach industrial production demand.But coal gasification temperature is higher, needs to consume more coals to maintain high-temperature gasification state, and the temperature worked off one's feeling vent one's spleen is higher, increased the energy loss of temperature-fall period.Therefore relatively conventional coal gasification, catalytic coal gasifaction have many advantages, and which main reason is that, coal gasification temperature can be significantly reduced in the presence of catalyst, holding is carried out at a lower temperature, while gas composition can also be adjusted, is referred to as third generation Coal Gasification Technology.
Alkali metal, alkaline-earth metal, transition metal（Fe、Co、Ni）Salt and its mixture there is significant facilitation effect to catalytic coal gasifaction.These catalyst mostly are solid particle, accelerate the carrying out of gasification reaction, therefore catalyst to have a significant impact to the effect of catalytic coal gasifaction with the hybrid mode of coal by being distributed in coal grain surface.Conventional hybrid mode has mechanical mixture and infusion process mixing.Although mechanical mixture operation is simple, not strong due to mixing uneven and between catalyst and coal dust adhesion, catalytic effect is as a result have impact on；Although infusion process mixing enables to catalytic component to a certain extent and is preferably distributed on coal sill, but when coal is contacted with impregnation liquid, due to dipping solution and the difference of coal surface nature and liquid-solid surface nature, solution is also different to the Wet Out of coal, and a large amount of hydrophobic group are contained on the surface of coal, with the intensification of degree of coalification, become the difficult moistening of comparison, therefore nor too preferable, this also constrains the raising of catalysis activity to dispersion effect of the catalytic component on coal sill to a certain extent.
The surface tension of aqueous solution is larger, it is impossible to effective wetting coal particle, and the addition of surfactant reduces can the surface tension and angle of wetting of aqueous solution.The characteristics of surfactant molecule structure is that it has unsymmetry, by the organic compound constituted with hydrophilic polar group and with hydrophobic non-polar group, according to remaining force-field theory, the hydrophobic group on coal surface interacts stronger with the hydrophobic group of surfactant, this causes the hydrophilic group of surfactant to stretch to solution, so as to increase its wettability to coal particle.Therefore, limitation present in the catalyst preparation process for current catalytic coal gasifaction, develops the new technology that catalytic component has preferable dispersion effect and preparation process not to take on coal sill, with important theoretical significance and actual application value.
The content of the invention
The present invention contains a large amount of hydrophobic group according to the surface of coal, catalyst solution is undesirable to coal particle surface moistening, the shortcomings of effectively can not being scattered on coal sill so as to cause existing catalytic coal gasifaction catalyst preparation process to there is catalytic component, there is the inherent structure feature of the class organic compound constituted by hydrophilic polar group and hydrophobic non-polar group there is provided a kind of utilization surface active agent composition, to improving the wettability of coal particle surface, method catalytic component simple and fast being distributed on coal sill, the process of sample preparation is greatly accelerated, and avoid the problem that conventional mechanical methods and infusion process equably will effectively can not mix between catalyst and coal sill.Carry out in catalytic coal gasification in fixed bed reactors, Activity Results show using catalyst preparation process provided by the present invention, the catalyst shows more excellent coal conversion ratio and methane-generated quantity.
The invention provides a kind of method for preparing catalyst for catalytic coal gasifaction preparing natural gas, it is characterized in that will be the alkali metal salt of solubility, surfactant soluble in water, stirring dissolves which, then again coal sill is added in above-mentioned solution, it is sufficiently stirred for making its mix homogeneously, active component is supported on coal sill, by processes such as centrifugation, washing and dryings, obtain the mixture of catalyst and coal sill, the particle diameter of the mixture is -100 mesh of 60 mesh, the loading of active component is metal quality and coal sill mass ratio, and loading is 6%-30%.
Usually, preparation method of the present invention is：The alkali metal salt of solubility, surfactant and coal sill are placed in deionized water, are sufficiently stirred for active component being supported on coal sill, centrifugation, washing and dried are crushed after tabletting and sieved for subsequent use.
The coal sill is brown coal, ub-bituminous coal, peat, bituminous coal, coke, petroleum coke or anthracite.
The alkali metal salt is Na2CO3、K2CO3, KCl, NaCl, Potassium Hydrogen Phthalate（KHP）In one kind, two or more combination.
The surfactant is dodecylbenzene sodium sulfonate（SDBS）, sodium lauryl sulphate（SDS）, Polyethylene Glycol series（PEG）In one kind, two or more combination.
A kind of typical laboratory preparation process of the present invention is as follows：
By 0.2-15 g soluble alkali metal salts, 0.1-
6 g surfactants are dissolved in deionized water, after stirring and dissolving, 1-20 g coal sills are added in above-mentioned solution, are sufficiently stirred for mixing which, are centrifuged, wash, process is dried in then going to baking oven, crush and be screened to-100 mesh of 60 mesh after tabletting.
The significant advantage presented by the present invention shows as：The technology of the present invention is in traditional catalytic coal gasifaction catalyst impregnating method preparation technique, add a small amount of surfactant, using the hydrophilic-hydrophobic construction featuress of surface active agent composition itself, improve the wettability of coal particle surface, so that coal sill upper surface functional group is had compared with strong interaction with catalytic component, not only avoid the problem that conventional mechanical methods and infusion process equably will effectively can not mix between catalyst and coal sill, the utilization rate of catalyst activity component is improve, and has greatly accelerated the process of sample preparation.The catalyst prepared using preparation technology provided by the present invention is applied in the reaction of fixed bed coal catalytic gasification preparing natural gas, as a result show the gasification temperature for significantly reducing coal sill, improve the gasification efficiency of coal sill, in addition, within the identical time, the technology of preparing provided using the present invention, the growing amount of methane prepare the methane content on catalyst higher than usual infusion process.This is conducive to the SNG processes for simplifying back segment operation, therefore this meets the demand that people are utilized to the clean and effective of coal resources to a certain extent, accelerates the paces of the commercial Application of China's catalytic coal gasifaction preparing natural gas technology.
Specific embodiment
Below by way of specific embodiment, the inventive method is described in detail in, but embodiment is merely to illustrate the present invention and is not meant to limit the scope of the invention.
Embodiment
1
1.0gPEG and 2.3gKHP is weighed, is dissolved in 30mL deionized waters, after stirring is completely dissolved, add 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample1, standby.
On the catalyst, efficiency of carbon con version versus time curve and CH4 accumulations amount of precipitation are shown in Table 1 respectively.
Embodiment
2
1.0gPEG, 0.2gSDBS and 2.3gKHP are weighed, is dissolved in 30mL deionized waters, after stirring is completely dissolved, add 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample2, standby.
On the catalyst, efficiency of carbon con version versus time curve and CH4 accumulations amount of precipitation are shown in Table 1 respectively.
Embodiment
3
5.0gPEG and 2.3gKHP is weighed, is dissolved in 30mL deionized waters, after stirring is completely dissolved, add 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample3, standby.
On the catalyst, efficiency of carbon con version versus time curve and CH4 accumulations amount of precipitation are shown in Table 1 respectively.
Embodiment
4
5.0gPEG, 0.2gSDBS and 2.3gKHP are weighed, is dissolved in 30mL deionized waters, after stirring is completely dissolved, add 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample4, standby.
Efficiency of carbon con version versus time curve and CH on the catalyst4Accumulation amount of precipitation is shown in Table 1 respectively.
Embodiment
5
0.2gSDBS and 2.3gKHP is weighed, is dissolved in 30mL deionized waters, after stirring is completely dissolved, add 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample5, standby.
Efficiency of carbon con version versus time curve and CH on the catalyst4Accumulation amount of precipitation is shown in Table 1 respectively.
Embodiment
6
Weigh 1.0gPEG and 1.1g
Na2CO3, it is dissolved in 30mL deionized waters, after stirring is completely dissolved, adds 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample6, standby.
Efficiency of carbon con version versus time curve and CH on the catalyst4Accumulation amount of precipitation is shown in Table 1 respectively.
Embodiment
7
Weigh 1.0gPEG and 0.9g
K2CO3, it is dissolved in 30mL deionized waters, after stirring is completely dissolved, adds 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample7, standby.
Efficiency of carbon con version versus time curve and CH on the catalyst4Accumulation amount of precipitation is shown in Table 1 respectively.
Embodiment
8
2.3gKHP is weighed, is dissolved in 30mL deionized waters, after stirring is completely dissolved, add 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample8, standby.
Efficiency of carbon con version versus time curve and CH on the catalyst4Accumulation amount of precipitation is shown in Table 1 respectively.
Embodiment
9
Weigh 1.1g Na2CO3, it is dissolved in 30mL deionized waters, after stirring is completely dissolved, adds 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample9, standby.
Efficiency of carbon con version versus time curve and CH on the catalyst4Accumulation amount of precipitation is shown in Table 1 respectively.
Embodiment
10
Weigh 0.9g K2CO3, it is dissolved in 30mL deionized waters, after stirring is completely dissolved, adds 3.0g bituminous coal, 50 DEG C of heated and stirred to go to baking oven and be dried to mix homogeneously, grinding is sieved, and is labeled as Sample10, standby.
Efficiency of carbon con version versus time curve and CH on the catalyst4Accumulation amount of precipitation is shown in Table 1 respectively.
Catalyst performance evaluation
The catalytic coal gasifaction preparing natural gas that the present invention is provided can be evaluated with the following method：
It is 32 mm in internal diameter, it is high by 800
In the rustless steel fixed bed reactors of mm, the pressure of reaction system is adjusted by Ar gas.Catalytic coal gasification condition：1.0 mL/min of de-ionized water flow rate, 973 K of reaction temperature, 3.4 MPa of reaction system pressure.
1 coal of table is changed into the conversion ratio of gas-phase product and methane accumulation growing amount
From table 1, in the reaction of catalytic coal gasifaction preparing natural gas, under same reaction process condition, add the catalyst of a small amount of surfactant（Sample1~2,Sample5~7）Coal be changed into the conversion ratio and methane-generated quantity that the conversion ratio and methane-generated quantity of gas-phase product are changed into gas-phase product far above the coal on other catalyst, coal wherein on Sample1 catalyst is changed into the conversion ratio and methane-generated quantity highest of gas-phase product, when reaction proceeds to 250 minutes, on the catalyst, coal is changed into the conversion ratio of gas-phase product and reaches 76.42%, and wherein the growing amount of methane is 5.39
mmol g-1, it is 3 times of the catalyst for being not added with surfactant, shows excellent methane performance processed.
Shown by the above results, in catalytic coal gasifaction field, alkali metal salt be can further improve as the methanation catalyst prepared catalytic gasification efficiency of catalytic coal gasifaction by the use of the technology of the present invention, it is changed on the conversion ratio and methane-generated quantity of gas-phase product in coal and shows preferable performance, the catalyst for catalytic coal gasifaction for utilizing the inventive method to prepare, low cost, preparation method are simple, show good using value.
Claims (7)
1. a kind of natural gas catalyst manufactured by coal, it is characterized in that the presoma of the catalyst is alkali metal salt, catalyst active component is distributed in atom level on coal sill, there is strong interaction to form mixture between catalyst and coal sill, the particle diameter of the mixture is -100 mesh of 60 mesh, the loading of active component is metal quality and carbon-based material mass ratio, and loading is 6%-30%.
2. a kind of preparation method of catalyst as claimed in claim 1, it is characterized in that, methods described comprises the steps, will be the alkali metal salt of solubility, surfactant soluble in water, and stirring dissolves which, then again coal sill is added in above-mentioned solution, it is sufficiently stirred for making its mix homogeneously, active component is supported on coal sill, obtains the mixture of catalyst and coal sill, by centrifugation, washing and be dried etc. process, after tabletting crush sieve it is prepared.
3. catalyst according to claim 1, it is characterised in that the loading of the active component is 10% ~ 25%.
4. the preparation method of catalyst according to claim 2, it is characterised in that described coal sill is the one kind in brown coal, ub-bituminous coal, bituminous coal, coke, petroleum coke or anthracite.
5. the preparation method of catalyst according to claim 2, it is characterised in that the alkali metal salt is Na2CO3、K2CO3, KCl, NaCl, Potassium Hydrogen Phthalate（KHP）In one kind, two or more combination.
6. the preparation method of catalyst according to claim 2, it is characterised in that the surfactant is dodecylbenzene sodium sulfonate（SDBS）, sodium lauryl sulphate（SDS）, Polyethylene Glycol series（PEG）In one kind, two or more combination.
7. the purposes of catalyst according to claim 1, it is characterised in that described catalytic coal gasifaction catalyst is used as preparing methane from coal, coal hydrogen, the catalyst of producing synthesis gas from coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510587811.0A CN106540730A (en) | 2015-09-16 | 2015-09-16 | A kind of natural gas catalyst manufactured by coal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510587811.0A CN106540730A (en) | 2015-09-16 | 2015-09-16 | A kind of natural gas catalyst manufactured by coal and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106540730A true CN106540730A (en) | 2017-03-29 |
Family
ID=58361456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510587811.0A Pending CN106540730A (en) | 2015-09-16 | 2015-09-16 | A kind of natural gas catalyst manufactured by coal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106540730A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722492A (en) * | 2017-04-21 | 2018-11-02 | 中国石油化工股份有限公司 | One kind being suitable for smokeless catalytic coal gasifaction catalyst and preparation method thereof |
| CN110075931A (en) * | 2019-04-26 | 2019-08-02 | 新奥科技发展有限公司 | A kind of catalyst carrying method of coal gasification |
| CN112044464A (en) * | 2020-08-27 | 2020-12-08 | 中国矿业大学 | Staged catalyst for fire district abandoned coal gasification operation and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804979A (en) * | 2010-04-07 | 2010-08-18 | 煤炭科学研究总院 | Coal-based carbon molecular sieve and preparation method thereof |
| CN103769200A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing sulfurization type hydro-cracking catalyst |
| CN104437563A (en) * | 2013-09-25 | 2015-03-25 | 中国石油化工股份有限公司 | Catalytic coal gasification catalyst and preparation method and application thereof |
-
2015
- 2015-09-16 CN CN201510587811.0A patent/CN106540730A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804979A (en) * | 2010-04-07 | 2010-08-18 | 煤炭科学研究总院 | Coal-based carbon molecular sieve and preparation method thereof |
| CN103769200A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing sulfurization type hydro-cracking catalyst |
| CN104437563A (en) * | 2013-09-25 | 2015-03-25 | 中国石油化工股份有限公司 | Catalytic coal gasification catalyst and preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722492A (en) * | 2017-04-21 | 2018-11-02 | 中国石油化工股份有限公司 | One kind being suitable for smokeless catalytic coal gasifaction catalyst and preparation method thereof |
| CN110075931A (en) * | 2019-04-26 | 2019-08-02 | 新奥科技发展有限公司 | A kind of catalyst carrying method of coal gasification |
| CN112044464A (en) * | 2020-08-27 | 2020-12-08 | 中国矿业大学 | Staged catalyst for fire district abandoned coal gasification operation and preparation method thereof |
| CN112044464B (en) * | 2020-08-27 | 2021-04-30 | 中国矿业大学 | Staged catalyst for fire district abandoned coal gasification operation and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104923234B (en) | Support type red mud composite catalyst for catalytic coal gasifaction and preparation method thereof | |
| CN106180747B (en) | A kind of palladium copper binary alloy nano material, preparation method and its CO is restored as catalyst electro-catalysis2Application | |
| CN105384162A (en) | Corncob-based porous carbon material, and preparation method and application thereof | |
| CN107519875B (en) | A kind of preparation method and application of carbon substrate Supported Co oxidate nano composite material | |
| CN108620089B (en) | Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation method and application thereof | |
| CN114031480B (en) | Method for preparing amyl alcohol by hydrogenation of 2-methylfuran through platinum-based catalyst | |
| CN106540730A (en) | A kind of natural gas catalyst manufactured by coal and preparation method thereof | |
| CN109201106A (en) | A kind of multi-stage porous HZSM-5 molecular sieve | |
| CN106283272A (en) | A kind of method that lower carbon number hydrocarbons catalytic pyrolysis prepares carbon fiber and hydrogen | |
| CN105921168A (en) | Preparation method of hydrodeoxidation isocatalyst, hydrodeoxidation isocatalyst and application thereof | |
| CN105126894A (en) | GaN catalyst as well as preparation method and application thereof in catalyzing oxidative dehydrogenation reaction of n-butane | |
| CN112717953A (en) | Carbon-based solid acid catalyst, preparation method and method for applying carbon-based solid acid catalyst to biomass hydrothermal conversion | |
| CN113751038A (en) | Fe prepared from waste biomass3C/C iron-based catalyst and preparation method and application thereof | |
| CN107311170B (en) | A kind of method and the active carbon preparing active carbon using slurry oil waste residue | |
| CN106040295A (en) | Preparation method for bio-based monodisperse carbon microsphere solid acid catalyst and application of bio-based monodisperse carbon microsphere solid acid catalyst in synthesis of biofuel | |
| CN111203224B (en) | Method for preparing green catalyst by using biomass tar and application | |
| CN104445145B (en) | A kind of simple method for preparing with hierarchical pore structure porous charcoal | |
| CN102875338A (en) | Method for preparing glycerol ether by catalytic glycerol ether reaction | |
| CN110385141A (en) | A kind of composite catalyst and preparation method thereof for the direct preparing aromatic hydrocarbon of synthesis gas | |
| KR20120094555A (en) | Novel metal catalyst supported on activated carbon aerogel, production method thereof and decomposition method of lignin compound using said catalyst | |
| CN108160090A (en) | It is a kind of using animal bone as solid alkali biodiesel catalyst of carrier and preparation method thereof | |
| CN101157028A (en) | Platinum carbon nanometer tube catalyzer for synthesizing citronellal | |
| CN107055507A (en) | A kind of preparation method of carbon molecular sieve | |
| CN106311339A (en) | Catalyst used for coal hydrogenation catalytic gasification, and preparation method and use thereof | |
| CN106589260B (en) | A kind of polycarboxylic acids slurries additive agent and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170329 |
|
| WD01 | Invention patent application deemed withdrawn after publication |