CN1151870C - Micropore carbon adsorbent for storing natural gas and its preparation method - Google Patents
Micropore carbon adsorbent for storing natural gas and its preparation method Download PDFInfo
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Abstract
The present invention relates to a new micropore carbon material for storing natural gas, particularly to a multi-micropore carbon adsorbent and a preparation method thereof. The BET specific surface area of the adsorbent can reach 2500 to 3500 m<2>/g, the pore volume of micropores reaches 1.5 to 1.8cm<3>/g, and the aperture is from 1 to 2 nm. The carbon adsorbent is an ideal material for adsorbing and storing natural gas. The preparation method of the present invention uses petroleum coke, lignin and pecan shells as raw materials, and adopts a compound activation agent method, a double-furnace and two-step activation technique and a coating molding technique to prepare the carbon adsorbent. The compound activation agents are prepared from KOH, a small amount of other metallic oxyhydroxides or metal chloride. The prepared adsorbent can be used for storing natural gas as automobile fuel or household fuel and storing and transporting natural gas without pipeline networks, and can also be used for adsorbing poisonous and harmful gas and used as coating additives for adsorbing wave, sound, etc.
Description
Invention field
The present invention relates to a kind of carbon absorbent and manufacture method thereof of rich micropore, relating in particular to a kind of is carbon absorbent of feedstock production natural gas-storing and preparation method thereof with petroleum coke, lignin, walnut shell.
Background of invention
Usually, the storage of natural gas and means of transportation are divided into three kinds: pipe network is carried (PNG), compressed natural gas (CNG), liquefied natural gas (LNG).Pipe network conveying at present is the main means of transportation of natural gas, and it is suitable for the natural gas accumulating of long distance.CNG is as the application of the existing certain scale of a kind of natural gas accumulating mode, and as gas-fueled vehicles etc., but its pressure store height (20MPa), the investment of compression device and storage facilities is big, but also has problem such as potential safety hazard.Kai Fa absorbed natural gas (ANG) technology is to utilize the adsorbent of high-ratio surface at mesolow (3.5～6.0MPa) times natural gas-storings in recent years.In theory, can reach the storage power density of CNG under 20MPa in 3.5MPa, natural gas storage power density 25 ℃ the time, but its key is the performance of natural gas adsorbent.
Before the present invention, having some patents of invention of putting down in writing relevant Preparation of Natural Gas Adsorbent method is disclosed, for example CN 1070846A (1993) and CN 1258638A (2000) have introduced the Preparation of Natural Gas Adsorbent method, its common feature is to adopt infusion process mixed material and chemical activating agent, adopt single one step of stove activation method to prepare powdered absorbent, the best activator and the ratio of charing raw material are 4: 1～5: 1 (weight ratio), and the binding agent compression forming is adopted in the moulding of adsorbent.Since raw material and activator at high temperature admixture and normal temperature under different fully, therefore, the obvious weak point of this technology is that priming reaction carries out easily under uneven mixing of materials state, directly cause the aggravation with side reaction of increasing of chemical activating agent consumption; From the adsorbent internal structure, be difficult to form the pore structure of stable uniform; And the adhesive moulding technique of powdered absorbent also because of using more binding agent (weight of binder accounts for split adsorbent weight 10～50%) in the forming process, causes the binding agent plug-hole easily, and then increases essential post processing measure.In addition, pore size distribution wider range of this class carbon adsorbent generally at 1～5nm, is not to be a kind of desirable natural gas adsorbent (Quinn etal people such as (U.S.5071820) thinks that the adsorbent pore size distribution of storing methane is advisable with 1～1.5nm).
It is raw material with synthesising macromolecule copolymer (as kayexalate) that WO97/07884 has introduced a kind of, 300～1000 ℃ of following charings, makes pore-size distribution by nitrogen protection between 0.4～2nm, the natural gas adsorbent of microporosity between 70～85%.It is raw material with vinylidene chloride (Vinylidene Chloride) that WO94/01714 has introduced a kind of, synthetic PVDC (polyvinylidene chloride), after charing at CO
2Effect prepare down the method for carbon molecular sieve adsorbent.This carbon molecular sieve has the pore-size distribution of 0.4～4nm.U.S.4999330 is a raw material with AX-21 adsorbent (a kind of petroleum coke system adsorbent) then, and the polyvinyl alcohol (PVA) of employing 1～10% is a binding agent, and adsorbent density is by the 0.3g/cm of powdery
3Be increased to 0.56～0.7 g/cm
3Though the unit volume methane storage capacity of adsorbent can be increased to 123.3g/l adsorbent (3.45MPa, 25 ℃) by 72.6, stops up because of the part of adsorbent micropore, its unit mass adsorbance drops to 14.8% (wt.) by 17.3% (wt.).
In a word, present micropore carbon adsorbent ubiquity pore-size distribution broad, the deficiency of microporosity lower (generally being lower than 75%), and, adopt prior preparation method,, also exist because activator level is higher for most of product, adopt the activating process of KOH also to produce a certain amount of simple substance potassium, be difficult to safety in production; And in the binding agent forming method, it is blocking microporous binding agent not only to occur, has reduced the unit mass adsorbance, and has used more binding agent, also causes cost to increase.
Summary of the invention
At present natural gas adsorption technology field above shortcomings, the invention provides a kind of micropore carbon adsorbent, it has narrow pore-size distribution and higher microporosity.
Micropore carbon adsorbent provided by the invention, its micro-pore diameter is distributed as 1～2nm, and microporosity (micro pore volume accounts for the percentage of total pore volume) is more than 90%.The BET specific surface can reach 2500～3500m
2/ g, micropore pore volume 1.5～1.8cm
3/ g.
This adsorbent can comprise powder adsorbent and type carbon adsorbent form, and powder adsorbent density is 0.18～0.30g/cm
3, type carbon adsorbent density is 0.35～0.65g/cm
3
The present invention also provides the preparation method of above-mentioned micropore carbon adsorbent, by adopting composite activating agent and twin furnace activating process, prepares the product of high-specific surface area, high microporosity, low pore-size distribution.
It is the composite activating agent of host that the present invention adopts with potassium hydroxide, with petroleum coke, lignin or walnut shell is raw material, frit reaction enters the high temperature furnace reaction again in low temperature oven earlier, by this two step of twin furnace priming reaction, the uniformity of realization response system, thus the adsorbent of making has the internal pore structure of stable uniform.
The present invention adopts Overmolded technology to prepare the type carbon adsorbent, has avoided the blocking microporous drawback of binding agent, has improved effective adsorbance of adsorbent.
Detailed Description Of The Invention
As previously mentioned, micropore carbon adsorbent provided by the invention, its micro-pore diameter is distributed as 1～2nm, and microporosity is more than 90%.The BET specific surface can reach 2500～3500m
2/ g, micropore pore volume 1.5～1.8cm
3/ g.
This adsorbent can comprise powder adsorbent and type carbon adsorbent form, and powder adsorbent density is 0.18～0.30g/cm
3, type carbon adsorbent density is 0.35～0.65g/cm
3
This preparation of adsorbent method is to be raw material with petroleum coke, lignin or walnut shell (carbide), may further comprise the steps:
(1) with described raw material pulverizing, sieve out 80～180 order powder, directly mix with the weight part ratio of composite activating agent with 1: 0.5～1: 4, in the low-temp reaction stove with 150～550 ℃ temperature frit reaction 1～3 hour, wherein, described composite activating agent is for being host with KOH, another kind of metal hydroxides except that metallic potassium or metal chloride are the activator that auxiliary agent is formed, and auxiliary agent content is 0.5～15% of KOH;
(2) material behind the low-temp reaction is put into high temperature reaction stove, reacted 0.5～2.5 hour down at 700～900 ℃, and course of reaction is carried out under nitrogen protection;
(3) the charcoal material after the pyroreaction washes with water earlier to neutrality, is salt acid soak 0.5～3hr of 0.01～0.5mol/l again with concentration, is that 100～150 ℃, vacuum are vacuum drying under 0.09～0.098Mpa condition in temperature then, makes powdered absorbent.
Among the above-mentioned preparation method of the present invention, adopted composite activating agent, promptly, with KOH is host, another kind of metal hydroxides or metal chloride except that metallic potassium, for example alkali metal beyond the potassium, the hydroxide or the chloride of alkaline-earth metal, the chloride that can also be subgroup metallic elements such as zinc, iron, copper is the activator that auxiliary agent is formed, and auxiliary agent content is 0.5～15% of KOH consumption, and the auxiliary compound that is suitable for can be selected from: Mg (OH)
2, Ca (OH)
2, NaOH, LiOH, NaCl, LiCl, MgCl
2, ZnCl
2, FeCl
3Or CuCl
2In one or more etc., the weight ratio of material powder and composite activating agent (activation ratio) is 1: 0.5～1: 4, preferably can be 1: 1.5～1: 3.
Preparation method of the present invention can comprise that also the powdered absorbent that will make places a kind of step that has the mould compression forming that coats box, promptly, with powdered absorbent compression moulding 2～10 minutes under 100～600MPa, at 100～150 ℃, dry 0.5～4hr is prepared into the cladded type carbon adsorbent under the vacuum degree condition of 0.09～0.098Mpa after the demoulding.
The clad material that the present invention adopts can be the material of thin tape pore, for example air-permeable paper, fine-meshed aluminium is thin or 200～500 eye mesh screens etc.Briquetting pressure is preferably 200～400Mpa.
Can draw from the above, the method for preparing micropore carbon adsorbent provided by the invention is to adopt multiplicity reactivation technology and twin furnace activating process, after activating earlier in advance, raw material enters the high temperature furnace activation again in low temperature oven, reaction system is finished under the condition of uniformity more, and in the inner pore structure that forms stable uniform of adsorbent, and another characteristics that adopt composite activating agent and twin furnace activating process are exactly no metallic potassium generation in the adsorbent preparation process, and the security of production process improves greatly.
Among the preparation method of the present invention, the composite activating agent use of can regenerating, washing water after high temperature carbonization reaction charcoal material washed is also reusable, and production cost is reduced, thereby has solved vital problem for the industrialization of high-ratio surface, rich micropore carbon adsorbent.
The present invention has adopted a kind of coating compression-molding method for the moulding of adsorbent, but not binding agent forming method of the prior art, its advantage is that the consumption of activator is reduced greatly, and this Overmolded technology is easy to the drawback of plug-hole when also having avoided using the binding agent moulding.
The rich micropore carbon adsorbent that adopts technology of the present invention to make generally has following performance characteristic: the BET specific area can reach 2500～3500m
2/ g, pore volume reaches 1.5～1.8cm
3/ g, bore dia mainly are distributed in 1～2nm, and microporosity accounts for more than 90%.At 25 ℃, under the 3.5MPa not the powder adsorbent of moulding effective adsorbance of methane is reached 13～18w%, volume adsorption reaches 90～110v/v; The type charcoal effective volume adsorbance that coats reaches 130～160v/v; At 25 ℃, under the 5.0MPa, the effective volume adsorbance of type carbon adsorbent can reach 160～180v/v.
The present invention prepares the raw material of adsorbent, and cheap and easy to get (lignin can prepare voluntarily, also commercially available), prepared adsorbent, both can be used for the no pipe network storage transportation of natural gas-storing as motor vehicle fuel or domestic fuel and natural gas, can be used to again adsorb toxic and harmful and be used to inhale ripple, sound-absorbing material etc., have broad application prospects as coating additive.
Embodiment
Below in conjunction with embodiment the present invention is further described, is intended to help the better understanding of reader technical scheme of the present invention, the practical range to technical solution of the present invention does not constitute any qualification.
Embodiment 1
With the petroleum coke fragmentation, be finely ground to 120～150 purpose powders, get 100 parts of these petroleum coke powdered carbons with 250 parts of KOH, 5 parts of Ca (OH)
2Solid mixture is as composite activating agent, mix the back and in the low-temperature activation stove, activate about 1.5 hours in advance, 300 ℃ of activation temperatures, material goes to the high-temperature activation stove again, activate about 1 hour down at 750 ℃, activation back material takes out and also washes with water to neutral (pH=7), is 0.01mol/l watery hydrochloric acid immersion about 30 minutes with concentration then, under 100 ℃ and 0.092Mpa vacuum dry 2 hours at last, promptly make powdered absorbent.
The BET specific area of measuring this adsorbent can reach 3450m
2/ g, pore volume reaches 1.75cm
3/ g, bore dia mainly are distributed in 1～2nm, and microporosity accounts for 93%, and bulk density reaches 0.29g/cm
3At 25 ℃, under the 3.5MPa not the powder adsorbent of moulding effective adsorbance of methane is reached 17.8w%, volume adsorption reaches 108v/v.
Embodiment 2
Get 100 part of 80～120 purpose petroleum coke powdered carbon, with 300 parts of KOH, 10 parts of Ca (OH)
2, 5 parts of ZnCl
2Solid mixture as composite activating agent.Mix the back and activate 2.5 hours in the low-temperature activation stove, 150 ℃ of activation temperatures go to the high-temperature activation stove again, activate 0.5 hour down at 790 ℃.After the activation material being taken out and washes with water to neutrality, is that 0.01mol/l watery hydrochloric acid soaked about 30 minutes with concentration then, and drying 2 hours under 120 ℃ and 0.092Mpa vacuum promptly makes the powdery natural gas adsorbent at last.
Performance of the adsorbent: the BET specific area can reach 3200m
2/ g, pore volume reaches 1.67cm
3/ g, bore dia mainly are distributed in 1～2nm, and microporosity accounts for 91%, and bulk density reaches 0.30g/cm
3At 25 ℃, under the 3.5MPa not the powder adsorbent of moulding effective adsorbance of methane is reached 16w%, volume adsorption reaches 98v/v.
Embodiment 3
With the petroleum coke fragmentation, be finely ground to 120～150 purpose powders, get 100 parts of petroleum coke powdered carbons with 380 parts of KOH, 2 parts of Ca (OH)
2, 10 parts of NaOH solid mixtures are as composite activating agent.Mix the back and activate about 1.5 hours in the low-temperature activation stove, 550 ℃ of activation temperatures go to the high-temperature activation stove again, activate about 1 hour down at 700 ℃.Activation back material takes out also and washes with water to neutrality, is that 0.01mol/l watery hydrochloric acid soaked 30 minutes with concentration then, and drying 2 hours under 100 ℃ and 0.092Mpa vacuum promptly makes the powdery natural gas adsorbent at last.
Performance: the BET specific area can reach 3450m
2/ g, pore volume reaches 1.78cm
3/ g, bore dia mainly are distributed in 1～2nm, and microporosity accounts for 95%, and bulk density reaches 0.29g/cm
3At 25 ℃, under the 3.5MPa not the powder adsorbent of moulding effective adsorbance of methane is reached 18w%, volume adsorption reaches 105v/v.
Embodiment 4
With the petroleum coke fragmentation, be finely ground to 120～150 purpose powders, get 100 parts of petroleum coke powdered carbons with 50 parts of KOH, 2 parts of ZnCl
2, 2 parts of Mg (OH)
2Solid mixture is as composite activating agent.Mix the back and activate about 2 hours in the low-temperature activation stove, 300 ℃ of activation temperatures go to the high-temperature activation stove again, activate about 2.5 hours down at 850 ℃.Activation back material takes out also and washes with water to neutrality, is that 0.01mol/l watery hydrochloric acid soaked 180 minutes with concentration then, and drying 2 hours under 100 ℃ and 0.092Mpa vacuum promptly makes the powdery natural gas adsorbent at last.
Performance: the BET specific area can reach 3300m
2/ g, pore volume reaches 1.62cm
3/ g, bore dia mainly are distributed in 1～2nm, and microporosity accounts for 90%, and bulk density reaches 0.30g/cm
3At 25 ℃, under the 3.5MPa not the powder adsorbent of moulding effective adsorbance of methane is reached 15.5w%, volume adsorption reaches 91v/v;
Embodiment 5
With the walnut shell charing, efflorescence becomes 120～150 purpose powders, gets 100 parts of these walnut shell charing powders, with 200 parts of KOH, 5 parts of Ca (OH)
2, 20 parts of FeCl
3Solid mixture as composite activating agent.Mix the back and activate about 1 hour in the low-temperature activation stove, 300 ℃ of activation temperatures go to the high-temperature activation stove again, activate about 1.5 hours down at 890 ℃.Activation back material takes out also and washes with water to neutrality, is that 0.1mol/l watery hydrochloric acid soaked 100 minutes with concentration then, and drying 1.5 hours under 120 ℃ and 0.095Mpa vacuum promptly makes the powdery natural gas adsorbent at last.
Performance: the BET specific area can reach 3100m
2/ g, pore volume reaches 1.62cm
3/ g, bore dia mainly are distributed in 1～2nm, and microporosity accounts for 90%, and bulk density reaches 0.24g/cm
3At 25 ℃, under the 3.5MPa not the powder adsorbent of moulding effective adsorbance of methane is reached 15.5w%, volume adsorption reaches 95v/v;
Embodiment 6
With the walnut shell charing, efflorescence becomes 120～150 purpose powders, gets 100 parts of walnut shell charing powders, with 150 parts of KOH, 10 parts of NaOH, 5 parts of MgCl
2Solid mixture as composite activating agent.Mix the back and activate about 1 hour in the low-temperature activation stove, 200 ℃ of activation temperatures go to the high-temperature activation stove again, activate 2.5 hours down at 890 ℃.Activation back material takes out also and washes with water to neutrality, is that 0.1mol/l watery hydrochloric acid soaked 100 minutes with concentration then, and drying 1.5 hours under 120 ℃ and 0.095Mpa vacuum promptly makes the powdery natural gas adsorbent at last.
Performance: the BET specific area can reach 3200m
2/ g, pore volume reaches 1.65cm
3/ g, bore dia mainly are distributed in 1～2nm, and microporosity accounts for 90%, and bulk density reaches 0.25g/cm
3At 25 ℃, under the 3.5MPa not the powder adsorbent of moulding effective adsorbance of methane is reached 14.5w%, volume adsorption reaches 96v/v;
Embodiment 7
With lignin oven dry, charing, efflorescence becomes 120～180 purpose powders, gets 100 parts of these lignin powdered carbons with 300 parts of KOH, 1 part of CuCl
2, 2 parts of Mg (OH)
2Solid mixture as composite activating agent.Mixture activates about 2.5 hours in the low-temperature activation stove, 400 ℃ of activation temperatures go to the high-temperature activation stove again, activates about 1.5 hours down at 900 ℃.Activation back material takes out also and washes with water to neutrality, is that 0.5mol/l watery hydrochloric acid soaked 120 minutes with concentration then, at last 150 ℃ with 0.097Mpa vacuum under vacuum drying 1 hour, promptly make the powdery natural gas adsorbent.
Performance: the BET specific area can reach 2700m
2/ g, pore volume reaches 1.52cm
3/ g, bore dia mainly are distributed in 1～2nm, and microporosity accounts for 95%, and bulk density reaches 0.19g/cm
3At 25 ℃, under the 3.5MPa not the powder adsorbent of moulding effective adsorbance of methane is reached 13.5w%, volume adsorption reaches 90v/v;
Embodiment 8
To be placed on by the powdered absorbent (as obtaining among the embodiment 1-4) of petroleum coke preparation in the coating filling box that a kind of usefulness 250 purpose stainless (steel) wires make, and will coat the cylinder mould that box places φ 50, in make-up machine, be squeezed to 400MPa pressure and kept 10 minutes, in mould, kept after the release 3 minutes and the demoulding, under 150 ℃ and 0.095Mpa vacuum dry 2 hours again, promptly obtain the type carbon adsorbent.
This type carbon adsorbent density is 0.65g/cm
3, 25 ℃, the methane effective volume adsorbance during 3.5MPa reaches 158v/v, and the methane effective volume adsorbance during 5.0MPa reaches 179v/v.
Embodiment 9
To be placed on by the powdered absorbent (as obtaining among the embodiment 7) of lignin preparation in the coating filling box that a kind of usefulness 400 purpose stainless (steel) wires make, and will coat the tetragonal prism mould that box places 50 * 50 * 100 (mm), in make-up machine, be squeezed to 500MPa pressure, and kept 8 minutes, in mould, kept after the release 5 minutes and demoulding, under 150 ℃ and 0.097Mpa vacuum dry about 2 hours again, promptly obtain the type carbon adsorbent.
This type carbon adsorbent density is 0.38g/cm
3, 25 ℃, the methane effective volume adsorbance during 3.5MPa reaches 151v/v.
Embodiment 10
In the ventilative coating box made of paper of the circle of walnut shell adsorbent (as obtaining in embodiment 5 or the 6) φ 20 that packs into, and be put in the mould of moulding compressor, pressurization 200MPa also kept under this pressure 5 minutes, in mould, keep 2 minutes demouldings again after the release, under 150 ℃ and the 0.097Mpa vacuum dry 1 hour, promptly obtain the cladded type carbon adsorbent.
This adsorbent density can reach 0.45g/cm
3, 25 ℃, the methane effective volume adsorbance during 3.5MPa reaches 155v/v.
Claims (8)
1, a kind of micropore carbon adsorbent, its micro-pore diameter is distributed as 1～2nm, and microporosity is more than 90%, BET specific area 2500～3500m
2/ g, micropore pore volume 1.5～1.8cm
3/ g, density was 0.18～0.30g/cm when this adsorbent was the powder adsorbent
3, density is 0.35～0.65g/cm during for the type carbon adsorbent
3
2, the preparation method of the described micropore carbon adsorbent of claim 1 is characterized in that being is raw material with petroleum coke, lignin or walnut shell, may further comprise the steps:
(1) with described raw material pulverizing, sieve out 80～180 order powder, directly mix with the weight part ratio of composite activating agent with 1: 0.5～1: 4, in the low-temp reaction stove with 150～550 ℃ temperature frit reaction 1～3 hour, wherein, described composite activating agent is for being host with KOH, metal hydroxides except that metallic potassium or metal chloride are the activator that auxiliary agent is formed, and auxiliary agent content is 0.5～15% of KOH;
(2) material behind the low-temp reaction is put into high temperature reaction stove, reacted 0.5～2.5 hour down at 700～900 ℃, and course of reaction is carried out under nitrogen protection;
(3) the charcoal material after the pyroreaction washes with water earlier to neutrality, is salt acid soak 0.5～3hr of 0.01～0.5mol/l again with concentration, is that 100～150 ℃, vacuum are vacuum drying under 0.09～0.098Mpa condition in temperature then, makes powdered absorbent.
3, the described preparation method of claim 2, it also further comprises powdered absorbent compression moulding 2～10 minutes under 100～600MPa, at 100～150 ℃, the down dry 0.5～4hr of the vacuum condition of 0.09～0.098Mpa prepares the coating compression forming step of cladded type carbon adsorbent after the demoulding.
4, claim 2 or 3 described preparation methods, wherein, the auxiliary agent in the composite activating agent comprises Mg (OH)
2, Ca (OH)
2, NaOH, LiOH, NaCl, LiCl, MgCl
2, ZnCl
2, FeCl
3Or CuCl
2In one or more.
5, the described preparation method of claim 3 wherein, coats in the compression forming, and the clad material of employing is a thin tape pore material.
6, the described preparation method of claim 5, wherein, described clad material comprises air-permeable paper, fine-meshed aluminium is thin or 200～500 eye mesh screens.
7, the described preparation method of claim 3, wherein, described briquetting pressure is 200～400Mpa.
8, the purposes of the described micropore carbon adsorbent of claim 1 in absorption and natural gas-storing.
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| CN101844069B (en) * | 2010-04-23 | 2013-03-27 | 成都益盛环境工程科技有限责任公司 | Method for preparing high surface-activity adsorbing carbon material through catalysis and activation synchronous process |
| CN108097206A (en) * | 2017-12-07 | 2018-06-01 | 浙江海洋大学 | A kind of preparation method of adsorbent to small molecule hydro carbons strong adsorption force |
| CN108097206B (en) * | 2017-12-07 | 2020-08-18 | 浙江海洋大学 | Preparation method of adsorbent with strong adsorption capacity on small molecular hydrocarbons |
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