CN1027234C - Natural gas adsorbent for store and its made method - Google Patents
Natural gas adsorbent for store and its made method Download PDFInfo
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- CN1027234C CN1027234C CN 92111246 CN92111246A CN1027234C CN 1027234 C CN1027234 C CN 1027234C CN 92111246 CN92111246 CN 92111246 CN 92111246 A CN92111246 A CN 92111246A CN 1027234 C CN1027234 C CN 1027234C
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Abstract
The present invention relates to an adsorbent for storing natural gas, and a production method thereof. The adsorbent has rich micropores and proper pore diameter. The adsorbent for storing natural gas is prepared from lignite, cannel and lignin, namely residues after wood hydrolysis. The adsorbent prepared by the present invention absorbs 17 to 24 wt% of natural gas; under the pressure of 6.0 MPas, the quantity of natural gas stored a steel bottle filled with the adsorbent is equivalent to the quantity of natural gas stored in an empty steel bottle with the same volume under the pressure of 15MPa. The production method of the adsorbent of the present invention is a chemical medicament activation method, and the mixed solution of alkaline earth metal hydroxide and metal chloride is used as chemical activation medicaments. The used medicaments can be circularly used after regeneration with a chemical method. The prepared adsorbent can be used for storing natural gas as automobile fuel or household fuel, and can be used for storing and transporting natural gas unsuitable for transportation by a pipeline in remote areas.
Description
The present invention relates to a kind of active carbon class material and manufacture method thereof, natural gas adsorbent for store is a kind of carbon class material of porous, belongs to a kind of active carbon of specific use.
At present, rock gas store high-pressure process and liquefaction process, but these methods investments are big, energy consumption is big, and dangerous, come natural gas-storing for overcoming above deficiency, the invention provides with sorbent.Now, sorbent can divide atresia and porous two big classes, and the specific surface of atresia sorbent is little, is not suitable for doing adsorbent; The specific surface of porous adsorbent is bigger, is applicable to adsorption seperation of gas mixer.These sorbents mainly contain active carbon, silica gel, activated alumina, porous glass etc.Its manufacturing process adopts the chemical agent activation method more, as US 3817874; US4082694 and US4642304 etc. all adopt chemical agent (KOH) activation method of single component to make the active carbon with high specific surface area of powdery, are applicable to water quality treatment agent, but are not suitable for the storage of rock gas, and cost an arm and a leg.
The purpose of this invention is to provide and a kind ofly both had absorbed natural gas high-ratio surface, and have suitable absorbed natural gas hole structure, make it not only have big absorbed natural gas ability, and have the new adsorbent of desorption ability fast.The method that the present invention adopts the chemical agent of many components and activator regenerative cycle to use reaches not only economy but also helps the purpose of industrial implementation.
The present invention is achieved in that with brown coal, cannel coal or lignin be the natural gas adsorbent that raw material makes, and has flourishing micropore and suitable pore-size distribution, and its micro-pore diameter is 10
Below; Median pore diameter is not more than 17
, to satisfy methane had both been had stronger adsorptive power, have desorption ability fast again.
The manufacture method of natural gas adsorbent of the present invention is: with the residue-lignin behind brown coal, cannel coal, the wood hydrolysis is raw material, 500～600 ℃ of following charing a few hours, make brown coal charcoal, cannel coal charcoal, lignin charcoal, obtain diameter less than 2 millimeters powdery carbon material through pulverizing, soak as the chemical activation medicament with the mixed solution of alkali metal hydroxide (as KOH, NaOH) and metal chloride (as ferric chloride, copper chloride).The ratio of KOH and NaOH can be in 0～100% range, but preferably uses mixed solution.The consumption of metal chloride is 0.1～5%(weight ratio of charcoal material), activation ratio (being the weight ratio of activator solution and charcoal material) is 1: 1～10: 1.After soaking a few hours, the charcoal material that has soaked is added in the revolving activation furnace, under inert gas (as nitrogen) atmosphere, be heated to 600～900 ℃ of activation temperatures.The soak time of keeping under this temperature is 0.5～3 hour.Cooling then.Cooled samples with water is washed till PH=7, then at 100～120 ℃ of dry down natural gas adsorbents that promptly made powdery in 2 hours.
After the sorbent of powdery added suitable Bond and water, in extrusion formula molding machine through knead, extruded moulding.Burl agent available carboxymethyl cellulose, polyvinyl alcohol or spent pulping liquor.Its consumption is 1～10%(weight ratio of powdered absorbent).The water yield is 50～300%(weight ratio of powdered absorbent,) sorbent after the moulding promptly makes granular natural gas adsorbent through 100～120 ℃ of down dry a few hours again, when being Bond with spent pulping liquor, need not add water in addition, its consumption is 100～300%(weight ratio of powdered absorbent).Sample after the moulding is handled through 500～600 ℃ of charings again, also can make the granular natural gas adsorbent of φ 2～5mm.
Can adopt natural gas adsorbent powdery or granular according to different purposes, adopt the sorbent of the present invention's preparation, its absorbed natural gas amount reaches the 17%(weight ratio) more than, be the stored amount of natural gas of container of having filled sorbent under the 6.0MPa is equivalent to not fill sorbent under 15MPa pressure the stored amount of natural gas of same volume container at gas pressure.But travel or, compare with the rock gas steam supply car of this storage with gasoline as household fuel, as rock gas during, inexpensive except having, octane value is high, cleaning, reduces to outside the advantages such as motor car engine wearing and tearing its CO as automotive fuel
2Discharge amount can reduce 30% than fuel-engined vehicle, the discharge amount of CO reduces 70%, helps to reduce the pollution of atmosphere, alleviates Global Greenhouse Effect.In addition, to the rock gas of remote districts and should not store and transportation with the also available natural gas adsorbent absorption of the defeated diffusing well rock gas of pipeline collection.
Fig. 1 is the natural gas adsorbent for store manufacturing process flow diagram.
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment 1: cannel coal is obtained the cannel coal charcoal through 500 ℃ of charings after 2 hours.Get 100 parts of cannel coal charcoals with KOH and contain a spot of FeCl
3Solution is as activator.Activator is 4: 1 with the ratio of material quantity.In revolving activation furnace, activate.Activation temperature is 700 ℃, and soak time is 1.5 hours.Activation back material takes out and washes with water to neutral (PH=7).Under the blanket of nitrogen under 120 ℃, drying promptly made the powdery natural gas adsorbent in 2 hours.
Embodiment 2: the powdery lignin obtains the lignin charcoal through 550 ℃ of charings after 2 hours.Get the activator mix that 100 parts of lignin charcoals and fresh activator and regenerative cycle are used.Fresh activator is 50%KOH, 50%NaOH and a spot of FeCl
3Mixed solution.The consumption of this solution is 1: 1 with the ratio of material quantity.Activate in revolving activation furnace, activation temperature is 850 ℃, and soak time is 1.5 hours.Wash with water after activation back material takes out to neutral (PH=7) and under 120 ℃ at N
2Drying promptly made the powdery natural gas adsorbent in 2 hours under the atmosphere.
Embodiment 3: brown coal were obtained the brown coal charcoal in 2 hours 550 ℃ of following charings.Get 100 parts of brown coal charcoals with KOH and contain small amount of Fe Cl
3Solution be activator.Its consumption is 4: 1 with the ratio of material quantity.Activate in revolving activation furnace, activation temperature is 800 ℃, soak time 1 hour.Wash with water after the taking-up to neutral (PH=7), and in 120 ℃ of following blanket of nitrogen dry 2 hours, the powdery natural gas adsorbent made.
Embodiment 4: getting 100 parts is the powdery natural gas adsorbent that raw material makes under optimum process condition by lignin, adds 1% polyvinyl alcohol (PVA) and 200 parts of water, and the even back of kneading is in the hydropress moulding.Sorbent after the moulding under 100 ℃, N
2Drying is 2 hours in the atmosphere, promptly makes cylindrical granulated sorbent.The bulk specific weight of granulated sorbent is 0.27g/cm
3
The performance of adsorbents adsorb rock gas is evaluated with weighting method and volumetric method respectively.Evaluation result is: adopt the weighting method evaluation, when gas pressure was 5.0MPa, the adsorbents adsorb amount of natural gas was the 22%(weight ratio), when pressure was 6.0MPa, the adsorbents adsorb amount of natural gas reached the 24%(weight ratio).
The evaluation of employing volumetric method, when gas pressure is 5.0MPa, filling the stored amount of natural gas of sorbent steel cylinder is equivalent to volume empty bottle stored amount of natural gas under 10.9MPa pressure, when natural atmospheric pressure is 6.0MPa, fills the stored amount of natural gas of sorbent steel cylinder and be equivalent to volume empty bottle stored amount of natural gas under 15MPa pressure.
Claims (6)
1, a kind of sorbent that is used for natural gas-storing is characterized in that having flourishing micropore, and its micro-pore diameter is 10
Below, median pore diameter is not more than 17
, be to soak in the activating agent promptly to make with the mixed solution of alkali metal hydroxide and metal chloride with carbonized material.
2, a kind of preparation of adsorbent method that is used for the natural gas-storing of claim 1 is characterized in that with brown coal, cannel coal or lignin be raw material, prepares by following step:
(A) under 500～600 ℃ with the raw material charing, obtain carbonized material;
(B) be to soak in the activating agent carbonized material with the mixed solution of alkali metal hydroxide and metal chloride, the chemical activation agent solution is 1: 1～10 with the ratio of charcoal material: 1(weight);
(C) be heated to 600～900 ℃ in the rotary furnace of the carbonized material that will soak under inert gas (as nitrogen) atmosphere, kept soak time 0.5～3 hour, then cooling;
(D) cooled charcoal material is washed with water, make PH=7, dry then, make the powdery natural gas adsorbent.
3, the preparation method of natural gas adsorbent for store according to claim 2 is characterized in that the powdered absorbent adding additives, and its consumption is 1～10%(weight ratio of powdered absorbent); Add water again, its consumption is 50%～300%(weight ratio of powdered absorbent), the moulding of in molding machine, kneading, and dry under 100～120 ℃, make granular natural gas adsorbent.
4,, it is characterized in that Bond is carboxymethyl cellulose, polyvinyl alcohol or spent pulping liquor according to the preparation method of claim 2 or 3 described natural gas adsorbent for store; When being Bond with spent pulping liquor, its consumption and powdered absorbent weight ratio are 100～300%.
5, the preparation method of natural gas adsorbent for store according to claim 2 is characterized in that alkali metal hydroxide is preferably KOH and NaOH mixed solution, and its ratio is in 0～100%(weight ratio).
6, the preparation method of natural gas adsorbent for store according to claim 2 is characterized in that metal chloride is FeCl
3Or CuCl
2, its consumption is 0.1～5%(weight ratio of charcoal material).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111246 CN1027234C (en) | 1992-10-12 | 1992-10-12 | Natural gas adsorbent for store and its made method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111246 CN1027234C (en) | 1992-10-12 | 1992-10-12 | Natural gas adsorbent for store and its made method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1070846A CN1070846A (en) | 1993-04-14 |
| CN1027234C true CN1027234C (en) | 1995-01-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92111246 Expired - Fee Related CN1027234C (en) | 1992-10-12 | 1992-10-12 | Natural gas adsorbent for store and its made method |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101913C (en) * | 1999-06-08 | 2003-02-19 | 天津大学 | Natural gas storage tank with adsorption matter and injection technology |
| CN102302925B (en) * | 2011-08-23 | 2013-06-12 | 华南理工大学 | Natural gas adsorbent, absorption tank utilizing natural gas adsorbent for storing and transporting natural gas, and method for absorbing, storing and transporting natural gas |
| CN105987278B (en) * | 2016-04-01 | 2018-09-11 | 石家庄安瑞科气体机械有限公司 | The filling of ANG storage tank adsorbents and localization method |
| KR102431511B1 (en) * | 2016-07-01 | 2022-08-12 | 인제비티 사우스 캐롤라이나, 엘엘씨 | Method for enhancing volumetric capacity in gas storage and release systems |
| CN112169763B (en) * | 2020-10-28 | 2023-04-07 | 怀化学院 | Nano porous adsorption material for virus protective mask and preparation method thereof |
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1992
- 1992-10-12 CN CN 92111246 patent/CN1027234C/en not_active Expired - Fee Related
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