CN102381713A - Hydrophobic silica gel for oil vapor recovery - Google Patents
Hydrophobic silica gel for oil vapor recovery Download PDFInfo
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- CN102381713A CN102381713A CN2011102522888A CN201110252288A CN102381713A CN 102381713 A CN102381713 A CN 102381713A CN 2011102522888 A CN2011102522888 A CN 2011102522888A CN 201110252288 A CN201110252288 A CN 201110252288A CN 102381713 A CN102381713 A CN 102381713A
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- Prior art keywords
- silica gel
- hydrophobic silicone
- raw material
- exsiccant
- stirring reaction
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 120
- 239000000741 silica gel Substances 0.000 title claims abstract description 120
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 106
- 238000011084 recovery Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000002994 raw material Substances 0.000 claims abstract description 66
- 239000002245 particle Substances 0.000 claims abstract description 65
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000011010 flushing procedure Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001296 polysiloxane Polymers 0.000 claims description 98
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 44
- 239000011148 porous material Substances 0.000 claims description 44
- 239000002250 absorbent Substances 0.000 claims description 25
- 238000000967 suction filtration Methods 0.000 claims description 24
- 239000002594 sorbent Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 150000007530 organic bases Chemical class 0.000 claims description 19
- 150000001721 carbon Chemical group 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- 239000012798 spherical particle Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000003209 petroleum derivative Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 104
- 239000003921 oil Substances 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229960001701 chloroform Drugs 0.000 description 22
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical group C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical group CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 12
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 12
- 230000000274 adsorptive effect Effects 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000003495 polar organic solvent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- 238000013459 approach Methods 0.000 description 8
- 238000003795 desorption Methods 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000005051 trimethylchlorosilane Substances 0.000 description 7
- AZBPJRLCFJLTRU-UHFFFAOYSA-N CC[SiH3].CN(C)C.O Chemical group CC[SiH3].CN(C)C.O AZBPJRLCFJLTRU-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical group C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 6
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical group C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- MZKZVFCVXHQHLC-UHFFFAOYSA-N CN(C)C.F[Si](F)(F)F Chemical group CN(C)C.F[Si](F)(F)F MZKZVFCVXHQHLC-UHFFFAOYSA-N 0.000 description 4
- PXJZCBUXFVZSLL-UHFFFAOYSA-N CO[SiH2]OC.C=CC Chemical group CO[SiH2]OC.C=CC PXJZCBUXFVZSLL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 208000012826 adjustment disease Diseases 0.000 description 4
- YCEQUKAYVABWTE-UHFFFAOYSA-N dichloro-methyl-prop-2-enylsilane Chemical group C[Si](Cl)(Cl)CC=C YCEQUKAYVABWTE-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
The invention provides a hydrophobic silica gel for oil vapor recovery. A preparation method of the hydrophobic silica gel comprises the following steps: first, using hydroscopic silica gel particles as a raw material and drying by heating under high temperature; second, mixing the dried raw material silica gel and organic solvent, which is dried in advance, adding a surface modifier and stirring for reaction; third, after stirring reaction in the second step, carrying out pumping filtration on the reaction products and flushing for several times by the dried solvent; fourth, drying the reaction products after flushing in the third step to obtain the hydrophobic silica gel particles. The hydrophobic silica gel obtained by the preparation method of the present invention has advantages of large specific surface area, good hydrophobicity, good adsorption / desorption effect on oil vapor and large intensity, does not rupture if put in water for 3 weeks and has no oil vapor adsorption quantity change if placed under an 80% RH humidity condition for two days.
Description
Technical field
The present invention relates to a kind of adsorbent that in the oil vapour absorbing recovery device, uses, relate in particular to a kind of hydrophobic silicone that in the oil vapour absorbing recovery device, uses.
Background technology
Oil product is defeated at collection, can discharge a large amount of oil vapour (VOC) in the refining, accumulating, sales process; When airborne oil vapour during by uviolizing; Meeting and oxygen reaction generate the oxygenant (is master's the general name with oxidizing substance with ozone, superoxide) that causes photo-chemical smog; The personnel health is worked the mischief, and simultaneously, this type oxygenant also can be further and oxynitride (NOx), oxysulfide reactions such as (SOx); Generation can cause nitric acid, the sulfuric acid of acid rain, thereby atmosphere is polluted.
Except the disadvantageous effect to environment and personnel health, the loss of oil vapour also can cause the minimizing of oil product quantity in the oil product, brings serious economy loss.For example, gasoline is produced from refinery and is arrived final user's hand, generally will be through four loading and unloading, and according to statistics, if do not take any measure, the wastage rate that gasoline causes because of volatilization will be up to 1.45%.
Consider from environmental angle and economic benefit angle; All need effectively reclaim, develop the method for the recovery of multiple oil vapour at present, wherein these oil vapours; Recovery technology based on transformation absorption (PSA); Because adsorption efficiency is high, operation and easy to maintenance, it is the most a kind of to become application.Reclaim in the technology in absorption method; Gac commonly used is as the oil vapour sorbent material; But gac is emitted a large amount of heats of adsorption during oil gas easily in absorption, and is particularly higher or when containing aldehyde, letones, active carbon bed very easily produces the phenomenon of local superheating when oil vapor concentration; Add that gac is inflammable and heat transfer efficiency is low, can bring disaster hidden-trouble.
Silica gel also is a kind of sorbent material commonly used, compares with gac, and it is big to have specific surface area, Controlled Pore Structure, and thermal conductivity is good, advantage such as do not burn.Because there is hydrophilic oh group in common silica gel surface (OH); Cause water vapour and oil vapour in the surperficial competitive adsorption of silica gel; Reduce adsorptive capacity and the physical strength that reduces silica gel to oil vapour; Therefore at first will guarantee the hydrophobicity of silica gel, the hydroxyl that promptly will make properties-correcting agent and silica gel surface hydrophilicity fully reacts and becomes hydrophobic grouping.
Secondly also to consider to influence the structural parameter of adsorbents adsorb performance; The absorption property of sorbent material depends primarily on specific surface area size and pore size distribution; The physical adsorption amount is directly proportional with the specific surface area of material basically, and reasonably pore size distribution will help sorbent material and after repeatedly recycling, keep higher adsorption rate.
Theoretical investigation thinks, when the aperture ratio of sorbing material was adsorbed big 3～4 times of molecular diameter, the reactive force of hole wall field (London force) mutual superposition increased surface and intermolecular interaction energy, can stronger adsorptive power be arranged to gas molecule.Therefore known oil molecule diameter, when the aperture of the sorbing material overwhelming majority is in 2nm～6nm scope, will possess more excellent oil vapour absorption property and higher desorption rate in 0.7～0.8nm scope.If the aperture is excessive, a little less than adsorbed molecules and the hole wall reactive force, easy desorption, but the sorbent material specific surface area is less, and adsorptive capacity maybe be very little; If the aperture is too small, hole wall surface and oil vapour interaction force are strong, and oil vapour is easily resident and cause the desorption difficulty.
There is a kind of preparation method of hydrophobically modified silica gel in prior art; It uses earlier the strong acid pickling activation with common Bibulous Silica Gel; Then under acid catalysis with multiple organic compound reaction, obtain hydrophobically modified silica gel through ageing, washing, dehydration, drying and other steps again, in this preparation method; Raw material silica gel absorbs water when acid-wash activation easily; Bulging force after the suction is destroyed the rigid structure of silica gel and produces fragmentation, and problems such as vacuum pump body obstruction take place when in pressure swing adsorption technique, using the pulverize powder easily;
The preparation method who also has a kind of hydrophobic silicone; It carries out hydrophobically modified in sol-gel method prepares the process of silica gel; At first acid is mixed with water glass; Process silica hydrosol, in silica hydrosol, add one or more organism, then through obtaining out-of-shape or even pulverous finished product after stirring, ageing, washing, the dehydration.This method needs to generate earlier silica hydrosol, and sample also needs the granulating and forming step as being used for transformation absorption.
Also there is a kind of preparation method who is used as the hydrophobic silicone of Zylox reinforcing filler; Its in the organosilicate-modified silicon water-sol pH be lower than 1 with strong inorganic acid in the presence of thermal treatment formation modification silicone-hydrogel; Then this aquogel system is contacted with silicoorganic compound in the presence of strong acid with silicoorganic compound; The modification silicone-hydrogel is carried out hydrophobic treatment, thereby obtain hydrophobically modified silica gel.The treating processes of this method is very complicated, operates manyly, and the sample particle diameter that obtains is little, forms Powderedly, also is not suitable for the oil gas pressure swing adsorption technique.
The preparation method who also has a kind of like this hydrophobic silicone; SiO 2 powder or moulding silica gel are warmed up to 550-700 ℃ specified temperature with 1-20 ℃/minute speed; And, in silicon-dioxide or silica gel, adding or not adding organic cpds at specified temperature maintenance specific time, the heat-treatment process of this method is complicated; Expense is higher, and the specific surface area of the hydrophobic silicone that makes has obviously and reduces.
Summary of the invention
Technical problem to be solved by this invention is to be to provide a kind of novel hydrophobic silicone that is used for the oil gas recovery; This hydrophobic silicone is a form of spherical particles; Overcome the hydrophobic silicone that the front the whole bag of tricks makes and significantly reduced with respect to raw material silica gel specific surface area, be prone to form the defective of pulverous hydrophobic silicone, the process for preparing this hydrophobic silicone is simple; This novel hydrophobic silicone has ethereal oil steam is had good adsorption and desorption performance; Product strength is high, meet water and do not break, and steam is to advantages such as the oil vapour Adsorption Effect are little.
In order to solve the problems of the technologies described above, the invention provides a kind of hydrophobic silicone that oil gas reclaims that is used for, the preparation method of said silica gel comprises the steps:
The first step, with the water-absorbent silica gel particle as raw material silica gel particle, at high temperature heating, drying;
Second step, the said raw material silica gel after the oven dry is mixed with pre-dry organic solvent, add surface-modifying agent, stirring reaction;
In the 3rd step, after the second step stirring reaction finishes, reaction product is carried out suction filtration, and repeatedly wash with the exsiccant solvent;
In the 4th step, through the reaction product after the flushing, obtain said hydrophobic silicone in dry the 3rd step;
Prepared hydrophobic silicone be shaped as form of spherical particles.
Wherein, the particle diameter of the hydrophobic silicone that is finally made is preferably 4-6mm, and specific surface area is preferably 350-880m
2/ g, the aperture is preferably 4nm-10nm, and with respect to the hydrophobic silicone solid particulate, the water vapor adsorption amount of the said hydrophobic silicone that finally makes is preferably 0.03-0.45g/g, and pore volume is 0.50-0.75cm
3/ g.
Wherein, Heating temperature is preferably about 2-9 hour said heat-up time for about 150 ℃ of about 115-in the said the first step.
Wherein, the time of stirring reaction is preferably about 2-11 hour in said second step, and the temperature of stirring reaction is about 20 ℃-50 ℃, and the said surface-modifying agent that adds in said second step can general formula be R
aH
bSiX
4-a-bOne or more mixing in the represented compound; Wherein R is selected from alkyl that comprises 1 to 12 carbon atom and the substituted alkyl of organo-functional group that comprises 1 to 12 carbon atom, and said alkyl is preferably saturated alkane base, alkylene, aryl, cycloalkyl group etc., and said organo-functional group is preferably saturated alkane base, alkylene, aryl, cycloalkyl group, amino etc.; X is selected from halogen and the alkoxyl group that comprises 1 to 12 carbon atom; A=0,1,2 or 3, b=0 or 1, a+b=1,2 or 3; When b=1, a+b=2 or 3.
Wherein, with respect to said raw material silica gel particulate amount, the add-on of said surface-modifying agent is 0.5wt%-20wt%.
Wherein, Exsiccant solvent in said the 3rd step is organic solvent and/or alcoholic solvent through processed, has also added the adjusting of organic bases promotion pH value in said the 3rd step, in said the 4th step; The exsiccant temperature is about 150 ℃ of about 60-, and the exsiccant time is about 2-5 hour.
For solving the problems of the technologies described above, the present invention also provides a kind of hydrophobic silicone that oil gas reclaims that is used for, and it is characterized in that the preparation method of said hydrophobic silicone comprises the steps:
The first step, with the water-absorbent silica gel particle as raw material silica gel particle, at high temperature heating, drying;
Second step, the said raw material silica gel after the oven dry is mixed with pre-dry organic solvent, slowly add surface-modifying agent, stirring reaction;
In the 3rd step, after the second step stirring reaction finishes, reaction product is carried out suction filtration, and repeatedly wash with the exsiccant solvent;
In the 4th step, through the reaction product after the flushing, obtain said hydrophobic silicone in dry the 3rd step;
Said raw material silica gel particle grain size is 3-6mm, and specific surface area is 450-700m
2/ g, the aperture is 3nm-7nm, pore volume is 0.38-0.90cm
3/ g;
The temperature of the heating in the said the first step is 115 ℃-130 ℃, and the time of heating is 2-4 hour;
The time of stirring reaction is 2-4 hour in said second step, and the temperature of stirring reaction is 20 ℃-50 ℃, and stirring reaction carries out under constant temperature;
The exsiccant temperature is 60 ℃-150 ℃ in said the 4th step, and the exsiccant time is 2-4 hour;
With respect to said raw material silica gel particulate amount, the add-on of surface-modifying agent is 0.5wt%-20wt% described in said second step.
With respect to the add-on of said surface-modifying agent, the add-on of organic bases is 25wt%-60wt% described in the 3rd step;
The hydrophobic silicone that is finally made be shaped as particulate state;
The particle diameter of the hydrophobic silicone that is finally made is preferably 4-6mm, and specific surface area is preferably 500-730m
2/ g, the aperture is preferably 4nm-7nm, and with respect to the hydrophobic silicone solid particulate, the water vapor adsorption amount of the said hydrophobic silicone that finally makes is preferably 0.03-0.45g/g.
For solving the problems of the technologies described above, the present invention also provides a kind of sorbent material, and said sorbent material is to be the mixture of staple by above-mentioned hydrophobic silicone, and mixture divides two-layer layout up and down, and the upper strata is that specific surface area is at 900-1500m
2/ g scope, pore size distribution be in the granular adsorption agent of 2-4nm scope, preferred columnar activated carbon, and lower floor is a hydrophobic silicone.
Wherein, with respect to the solid weight of said sorbent material, the content of said hydrophobic silicone is preferably 30%-70%, and most preferred content is 40%-60%.
The present invention also provides the application at least one process of production, transportation and storage of above-mentioned hydrophobic silicone or sorbent material petroleum products.
The present invention also provides above-mentioned hydrophobic silicone or the application of sorbent material in the pressure-swing adsorption process of oil vapour.
The hydrophobic silicone that adopts preparation method of the present invention to obtain is a form of spherical particles, has that specific surface area is big, hydrophobicity good, an advantage such as effective and intensity is big to the absorption/desorption of oil vapour, and product is placed in water and do not broken in 3 weeks; 80%RH humidity condition held two days,, can extraordinaryly be applied to pressure swing adsorption technique to the not influence basically of oil vapour adsorptive capacity; Preventing vacuum pump body stops up; Form the water-sol and available technology adopting is sour with the water glass reaction, and then form gel, the dewatering silica gel of method preparations such as employing strong acid pickling silica gel is Powdered; Vacuum pump body taking place easily stop up, is inappropriate for pressure swing adsorption technique.
Embodiment
The invention provides a kind of preparation method who is used for the hydrophobic silicone of oil gas recovery, said method comprises the steps:
The first step, with the water-absorbent silica gel particle as raw material silica gel particle, at high temperature heating, drying;
Second step, the said raw material silica gel after the oven dry is mixed with pre-dry organic solvent, add surface-modifying agent, stirring reaction;
In the 3rd step, after the second step stirring reaction finishes, reaction product is carried out suction filtration, and repeatedly wash with the exsiccant solvent;
In the 4th step, through the reaction product after the flushing, obtain said hydrophobic silicone in dry the 3rd step.
Wherein, further preferred, the preparation method of this hydrophobic silicone only is made up of above-mentioned four steps.
What wherein, said water-absorbent silica gel particle can adopt is any water-absorbent silica gel particle on sale on the market.
Wherein, said raw material silica gel particle grain size is preferably 3-6mm, and said raw material silica gel particulate specific surface area is preferably 320-920m
2/ g further is preferably 450-700m
2/ g, said raw material silica gel particulate aperture is preferably 3nm-10nm, further is preferably 3nm-7nm, and said raw material silica gel particulate pore volume is preferably 0.38-0.90cm
3/ g further is preferably 0.55-0.80cm
3/ g.
Wherein, the oven dry under the high temperature in the said the first step is preferably dried in vacuum drying oven, and the temperature of said heating is preferably 115 ℃-150 ℃, and further preferred 115 ℃-130 ℃, the time of said heating is preferably 2-9 hour, further preferred 2-4 hour.
Wherein, The exsiccant organic solvent that uses in said second step is preferably non-polar organic solvent; Further be preferably one or more mixing in hexanaphthene, chloroform, methylene dichloride, benzene and the toluene; Said exsiccant organic solvent can adopt conventional drying means, as puts into siccative etc. and carry out drying.
Wherein, the weight ratio of the add-on of said exsiccant organic solvent and silica gel raw material is preferably 1.2: 1-3: 1, further be preferably 1.5: 1-2: 1.
Wherein, the time of stirring reaction is preferably 2-11 hour in said second step, further is preferably 2-4 hour.
Wherein, be stirring reaction under constant temperature in said second step, the stirring reaction temperature is preferably 20 ℃-50 ℃.
Wherein, the said surface-modifying agent that adds in said second step is one or more mixing in the silicoorganic compound, and general formula is R
aH
bSiX
4-a-b, wherein R is selected from alkyl that comprises 1 to 12 carbon atom and the substituted alkyl of organo-functional group that comprises 1 to 12 carbon atom, and said alkyl is preferably saturated alkane base, alkylene, aryl, cycloalkyl group etc.; Said organo-functional group is preferably saturated alkane base, alkylene, aryl, cycloalkyl group, amino etc., and X is selected from halogen and the alkoxyl group that comprises 1 to 12 carbon atom, a=0,1,2 or 3; B=0 or 1, a+b=1,2 or 3, wherein; When b=1, a+b=2 or 3.Preferably include trimethylchlorosilane; Trimethylammonium silicon fluoride, dimethyldichlorosilane(DMCS), diphenyl dichlorosilane, diethyl dichlorosilane, allyl methyl dichlorosilane, dichloromethyl phenylsilane, hexamethyldisilazane, trimethylammonium oxygen ethylsilane, methyl ethylene dimethoxy silane, amyl group dimethyl dichlorosilane (DMCS) etc.
Wherein, with respect to raw material silica gel particulate amount, the add-on of said surface-modifying agent is preferably 0.5wt%～20wt%, more preferably 2.0wt%～20wt%.
Wherein, adding surface-modifying agent in said second step is under constant temperature, to add slowly, and described constant temp scope is preferably 20 ℃-50 ℃.
Wherein, the reaction vessel of the stirring reaction in said second step is preferably there-necked flask, and the preferred sealing effectiveness of there-necked flask is good, thereby guarantees not have in the reaction process infiltration of water.
Wherein, in said the 3rd step reaction product being adopted the purpose of exsiccant solvent washing is to remove the pH value of unreacted properties-correcting agent and adjustment reaction product, the pH value of adjusted reaction product is reached or approaches neutrality, preferably approaches 7.
Wherein, the exsiccant solvent in said the 3rd step is preferably organic solvent and/or alcoholic solvent through processed, further is preferably one or more mixing in hexanaphthene, chloroform, methylene dichloride, benzene, toluene, methyl alcohol, ethanol and the propyl alcohol.
Wherein, In the 3rd step, adopt in the process of exsiccant non-polar organic solvent flushing; Further preferably add the adjusting that a certain amount of organic bases promotes the pH value of reaction product, described organic bases is preferably one or more the combination in diethylamine, triethylamine or the pyridine.
Wherein, with respect to the add-on of surface-modifying agent, the add-on of organic bases is preferably 25wt%-60wt% in said the 3rd step, further is preferably 25wt%-50wt%.
Wherein, the drying in said the 4th step is preferably dry in vacuum drying oven, and said exsiccant temperature is preferably 60 ℃-150 ℃, and further preferred 80 ℃-110 ℃, the said exsiccant time is preferably 2-4 hour.
Through the flushing in said the 3rd step and the 4th step, suction filtration and drying process have been removed unreacted surface-modifying agent and remaining organic solvent behind the stirring reaction.
The present invention also provides a kind of preparation method who is used for the hydrophobic silicone of oil gas recovery, and said method comprises the steps:
The first step, with the water-absorbent silica gel particle as raw material silica gel particle, at high temperature heating, drying;
Second step, the said raw material silica gel after the oven dry is mixed with pre-dry organic solvent, slowly add surface-modifying agent, stirring reaction;
In the 3rd step, after the second step stirring reaction finishes, reaction product is carried out suction filtration, and repeatedly wash with the exsiccant solvent;
In the 4th step, through the reaction product after the flushing, obtain said hydrophobic silicone in dry the 3rd step;
Said raw material silica gel particle grain size is 3-6mm, and specific surface area is 450-700m
2/ g, the aperture is 3nm-7nm, pore volume is 0.55-0.80cm
3/ g;
The temperature of the heating in the said the first step is 115 ℃-150 ℃, and the time of heating is 2-4 hour;
The time of stirring reaction is 2-4 hour in said second step, and the temperature of said stirring reaction is 20 ℃-50 ℃, and stirring reaction carries out under constant temperature;
The exsiccant temperature is 60 ℃-150 ℃ in said the 4th step, and the exsiccant time is 2-4 hour;
With respect to said raw material silica gel particulate amount, the add-on of said surface-modifying agent is 0.5wt%～20wt%, more preferably 2.0wt%～20wt%.
Wherein, further preferred, the preparation method of this hydrophobic silicone only is made up of above-mentioned four steps.
What wherein, said water-absorbent silica gel particle can adopt is any water-absorbent silica gel particle on sale on the market.
Wherein, the weight ratio of the add-on of said exsiccant organic solvent and silica gel raw material is preferably 1.2: 1-3: 1, further be preferably 1.5: 1-2: 1.
Wherein, The exsiccant organic solvent that uses in said second step is preferably non-polar organic solvent; Further be preferably one or more mixing in hexanaphthene, chloroform, methylene dichloride, benzene and the toluene; Said exsiccant organic solvent can adopt conventional drying means, as puts into siccative etc. and carry out drying.
Wherein, the said surface-modifying agent that adds in said second step is one or more mixing in the silicoorganic compound, and general formula is R
aH
bSiX
4-a-b, wherein R is selected from alkyl that comprises 1 to 12 carbon atom and the substituted alkyl of organo-functional group that comprises 1 to 12 carbon atom, and said alkyl is preferably saturated alkane base, alkylene, aryl, cycloalkyl group etc.; Said organo-functional group is preferably saturated alkane base, alkylene, aryl, cycloalkyl group, amino etc., and X is selected from halogen and the alkoxyl group that comprises 1 to 12 carbon atom, a=0,1,2 or 3; B=0 or 1, a+b=1,2 or 3, wherein; When b=1, a+b=2 or 3.Preferably include trimethylchlorosilane; Trimethylammonium silicon fluoride, dimethyldichlorosilane(DMCS), diphenyl dichlorosilane, diethyl dichlorosilane, allyl methyl dichlorosilane, dichloromethyl phenylsilane, hexamethyldisilazane, trimethylammonium oxygen ethylsilane, methyl ethylene dimethoxy silane, amyl group dimethyl dichlorosilane (DMCS) etc.
Wherein, the reaction vessel of the stirring reaction in said second step is preferably there-necked flask, and the preferred sealing effectiveness of there-necked flask is good, thereby guarantees not have in the reaction process infiltration of water.
Wherein, in said the 3rd step reaction product being adopted the purpose of exsiccant solvent washing is to remove the pH value of unreacted properties-correcting agent and adjustment reaction product, the pH value of adjusted reaction product is reached or approaches neutrality, preferably approaches 7.
Wherein, the exsiccant solvent in said the 3rd step is preferably organic solvent and/or alcoholic solvent through processed, further is preferably one or more mixing in hexanaphthene, chloroform, methylene dichloride, benzene, toluene, methyl alcohol, ethanol and the propyl alcohol.
Wherein, In the 3rd step, adopt in the process of exsiccant non-polar organic solvent flushing; Further preferably add the adjusting that a certain amount of organic bases promotes the pH value of reaction product, described organic bases is preferably one or more the combination in diethylamine, triethylamine or the pyridine.
Wherein, with respect to the add-on of surface-modifying agent, the add-on of organic bases is preferably 25wt%-60wt% in said the 3rd step.
Through after organism is reacted as the hydroxyl of surface-modifying agent and water-absorbent silica gel particle surface, make the very strong silicon hydroxyl of wetting ability change into group, thereby obtain hydrophobic silicone among the present invention with hydrophobic property.
The present invention also provides a kind of hydrophobic silicone that oil gas reclaims that is used for, and the preparation method of said silica gel comprises the steps:
The first step, with the water-absorbent silica gel particle as raw material silica gel particle, at high temperature heating, drying;
Second step, the said raw material silica gel after the oven dry is mixed with pre-dry organic solvent, add surface-modifying agent, stirring reaction;
In the 3rd step, after the second step stirring reaction finishes, reaction product is carried out suction filtration, and repeatedly wash with the exsiccant solvent;
In the 4th step, through the reaction product after the flushing, obtain said hydrophobic silicone in dry the 3rd step;
Prepared hydrophobic silicone be shaped as form of spherical particles.
Wherein, further preferred, the preparation method of this silica gel only is made up of above-mentioned four steps.
What wherein, said water-absorbent silica gel particle can adopt is any water-absorbent silica gel particle on sale on the market.
Wherein, said raw material silica gel particle grain size is preferably 3-6mm, and said raw material silica gel particulate specific surface area is preferably 320-920m
2/ g further is preferably 450-700m
2/ g, said raw material silica gel particulate aperture is preferably 3nm-10nm, further is preferably 3nm-7nm, and said raw material silica gel particulate pore volume is preferably 0.35-0.85cm
3/ g further is preferably 0.55-0.80cm
3/ g.
The particle diameter of the hydrophobic silicone that wherein, is finally made is preferably 4-6mm.
The specific surface area of the hydrophobic silicone that wherein, is finally made is preferably 350-880m
2/ g further is preferably 500-730m
2/ g.
Wherein, the aperture of the hydrophobic silicone that is finally made is preferably 4nm-10nm, further is preferably 4nm-7nm, and pore volume is preferably 0.50-0.75cm
3/ g further is preferably 0.55-0.70cm
3/ g.
Wherein, with respect to the hydrophobic silicone solid particulate, the water vapor adsorption amount of the said hydrophobic silicone that finally makes is preferably 0.03-0.45g/g.
Wherein, the oven dry under the high temperature in the said the first step is preferably dried in vacuum drying oven, and the temperature of said heating is preferably 115 ℃-150 ℃, and further preferred 115 ℃-130 ℃, the time of said heating is preferably 2-9 hour, further preferred 2-4 hour.
Wherein, The exsiccant organic solvent that uses in said second step is preferably non-polar organic solvent; Further be preferably one or more mixing in hexanaphthene, chloroform, methylene dichloride, benzene and the toluene; Said exsiccant organic solvent can adopt conventional drying means, as puts into siccative etc. and carry out drying.
Wherein, the weight ratio of the add-on of said exsiccant organic solvent and silica gel raw material is preferably 1.2: 1-3: 1.
Wherein, the time of stirring reaction is preferably 2-11 hour in said second step, further is preferably 2-4 hour.
Wherein, stirring reaction carries out under constant temperature in said second step, and said stirring reaction temperature is preferably 20 ℃-50 ℃.
Wherein, the said surface-modifying agent that adds in said second step is one or more mixing in the silicoorganic compound, and general formula is R
aH
bSiX
4-a-b, wherein R is selected from alkyl that comprises 1 to 12 carbon atom and the substituted alkyl of organo-functional group that comprises 1 to 12 carbon atom, and said alkyl is preferably saturated alkane base, alkylene, aryl, cycloalkyl group etc.; Said organo-functional group is preferably saturated alkane base, alkylene, aryl, cycloalkyl group, amino etc., and X is selected from halogen and the alkoxyl group that comprises 1 to 12 carbon atom, a=0,1,2 or 3; B=0 or 1, a+b=1,2 or 3, wherein; When b=1, a+b=2 or 3.Preferably include trimethylchlorosilane; Trimethylammonium silicon fluoride, dimethyldichlorosilane(DMCS), diphenyl dichlorosilane, diethyl dichlorosilane, allyl methyl dichlorosilane, dichloromethyl phenylsilane, hexamethyldisilazane, trimethylammonium oxygen ethylsilane, methyl ethylene dimethoxy silane, amyl group dimethyl dichlorosilane (DMCS) etc.
Wherein, with respect to raw material silica gel particulate amount, the add-on of said surface-modifying agent is preferably 0.5wt%～20wt%, more preferably 2.0wt%～20wt%.
Wherein, adding surface-modifying agent in said second step is under constant temperature, to add slowly, and described constant temp scope is preferably 20 ℃-50 ℃.
Wherein, in said the 3rd step reaction product being adopted the purpose of exsiccant solvent washing is to remove the pH value of unreacted properties-correcting agent and adjustment reaction product, the pH value of adjusted reaction product is reached or approaches neutrality, preferably approaches 7.
Wherein, the exsiccant solvent in said the 3rd step is preferably organic solvent and/or alcoholic solvent through processed, further is preferably one or more mixing in hexanaphthene, chloroform, methylene dichloride, benzene, toluene, methyl alcohol, ethanol and the propyl alcohol.
Wherein, In the 3rd step, adopt in the process of exsiccant non-polar organic solvent flushing; Further preferably add the adjusting that a certain amount of organic bases promotes the pH value of reaction product, described organic bases is preferably one or more the combination in diethylamine, triethylamine or the pyridine.
Wherein, with respect to the add-on of surface-modifying agent, the add-on of organic bases is preferably 25wt%-60wt% in said the 3rd step, further is preferably 25wt%-50wt%.
Wherein, the drying in said the 4th step is preferably dry in vacuum drying oven, and said exsiccant temperature is preferably 60 ℃-150 ℃, and further preferred 80 ℃-110 ℃, the said exsiccant time is preferably 2-4 hour.
Through the flushing in said the 3rd step and the 4th step, suction filtration and drying process have been removed unreacted surface-modifying agent and remaining organic solvent behind the stirring reaction.
The present invention also provides a kind of hydrophobic silicone that oil gas reclaims that is used for, and the preparation method of said silica gel comprises the steps:
The first step, with the water-absorbent silica gel particle as raw material silica gel particle, at high temperature heating, drying;
Second step, the said raw material silica gel after the oven dry is mixed with pre-dry organic solvent, slowly add surface-modifying agent, stirring reaction;
In the 3rd step, after the second step stirring reaction finishes, reaction product is carried out suction filtration, and repeatedly wash with the exsiccant solvent;
In the 4th step, through the reaction product after the flushing, obtain said hydrophobic silicone in dry the 3rd step;
Prepared hydrophobic silicone be shaped as form of spherical particles;
Said raw material silica gel particle grain size is 3-6mm, and specific surface area is 450-700m
2/ g, the aperture is 3nm-7nm, pore volume is 0.55-0.80cm
3/ g;
The temperature of the heating in the said the first step is 115 ℃-130 ℃, and the time of heating is 2-4 hour;
The time of stirring reaction is 2-4 hour in said second step, and the temperature of said stirring reaction is 20 ℃-50 ℃, and said stirring reaction carries out under constant temperature;
The exsiccant temperature is 60 ℃-150 ℃ in said the 4th step, and the exsiccant time is 2-4 hour;
With respect to said raw material silica gel particulate amount, the add-on of surface-modifying agent is 0.5wt%-20wt% described in said second step;
With respect to the add-on of said surface-modifying agent, the add-on of organic bases is 25wt%-60wt% described in the 3rd step;
The hydrophobic silicone that is finally made that is finally made be shaped as form of spherical particles;
The particle diameter of the hydrophobic silicone that is finally made is preferably 4-6mm, and specific surface area is preferably 500-730m
2/ g, the aperture is preferably 4nm-7nm, and pore volume is 0.55-0.70cm
3/ g, with respect to the hydrophobic silicone solid particulate, the water vapor adsorption amount of the said hydrophobic silicone that finally makes is preferably 0.03-0.45g/g.
Wherein, In the 3rd step, adopt in the process of exsiccant non-polar organic solvent flushing; Further preferably add the adjusting that a certain amount of organic bases promotes the pH value of reaction product, described organic bases is preferably one or more the combination in diethylamine, triethylamine or the pyridine.
Wherein, further preferred, the preparation method of this silica gel only is made up of above-mentioned four steps.
What wherein, said water-absorbent silica gel particle can adopt is any water-absorbent silica gel particle on sale on the market.
Wherein, the weight ratio of the add-on of said exsiccant organic solvent and silica gel raw material is preferably 1.2: 1-3: 1, further preferred 1.5: 1-2: 1.
Wherein, The exsiccant organic solvent that uses in said second step is preferably non-polar organic solvent; Further be preferably one or more mixing in hexanaphthene, chloroform, methylene dichloride, benzene and the toluene; Said exsiccant organic solvent can adopt conventional drying means, as puts into siccative etc. and carry out drying.
Wherein, the said surface-modifying agent that adds in said second step is one or more mixing in the silicoorganic compound, and general formula is R
aH
bSiX
4-a-b, wherein R is selected from alkyl that comprises 1 to 12 carbon atom and the substituted alkyl of organo-functional group that comprises 1 to 12 carbon atom, and said alkyl is preferably saturated alkane base, alkylene, aryl, cycloalkyl group etc.; Said organo-functional group is preferably saturated alkane base, alkylene, aryl, cycloalkyl group, amino etc., and X is selected from halogen and the alkoxyl group that comprises 1 to 12 carbon atom, a=0,1,2 or 3; B=0 or 1, a+b=1,2 or 3, wherein; When b=1, a+b=2 or 3.Preferably include trimethylchlorosilane; Trimethylammonium silicon fluoride, dimethyldichlorosilane(DMCS), diphenyl dichlorosilane, diethyl dichlorosilane, allyl methyl dichlorosilane, dichloromethyl phenylsilane, hexamethyldisilazane, trimethylammonium oxygen ethylsilane, methyl ethylene dimethoxy silane, amyl group dimethyl dichlorosilane (DMCS) etc.
Wherein, the reaction vessel of the stirring reaction in said second step is preferably there-necked flask, and the preferred sealing effectiveness of there-necked flask is good, thereby guarantees not have in the reaction process infiltration of water.
Wherein, in said the 3rd step reaction product being adopted the purpose of exsiccant solvent washing is to remove the pH value of unreacted properties-correcting agent and adjustment reaction product, the pH value of adjusted reaction product is reached or approaches neutrality, preferably approaches 7.
Wherein, the exsiccant solvent is preferably organic solvent and/or alcoholic solvent through processed in said the 3rd step, further is preferably one or more mixing in hexanaphthene, chloroform, methylene dichloride, benzene, toluene, methyl alcohol, ethanol and the propyl alcohol.
Wherein, In the 3rd step, adopt in the process of exsiccant non-polar organic solvent flushing; Further preferably add the adjusting that a certain amount of organic bases promotes the pH value of reaction product, described organic bases is preferably one or more the combination in diethylamine, triethylamine or the pyridine.
With respect to said raw material silica gel particulate amount, the add-on of surface-modifying agent further is preferably 2.0wt%-20wt% described in said second step.
Wherein, with respect to the add-on of said surface-modifying agent, the add-on of organic bases is preferably 25wt%-50wt% in said the 3rd step.
The present invention also provides a kind of sorbent material, it is characterized in that: said sorbent material is to be the mixture of staple by above-mentioned hydrophobic silicone, and mixture divides two-layer layout up and down, and the upper strata is that specific surface area is at 900-1500m
2/ g scope, pore size distribution be in the granular adsorption agent of 2-4nm scope, preferred columnar activated carbon, and lower floor is a hydrophobic silicone.
Wherein, with respect to the solid weight of said sorbent material, the content of said hydrophobic silicone is preferably 30%-70%, and most preferred content is 40%-60%.
The present invention also provides the application of preparation method at least one process of production, transportation and storage of petroleum products of above-mentioned hydrophobic silicone.
The preparation method that the present invention also provides above-mentioned hydrophobic silicone is to the application in the modifying process of the material that contains silica gel.
The present invention also provides above-mentioned hydrophobic silicone and the application of sorbent material at least one process of production, transportation and storage of petroleum products.
The present invention also provides the application of preparation method in the oil vapour pressure-swing adsorption process of above-mentioned hydrophobic silicone.
The present invention also provides above-mentioned hydrophobic silicone and the application of sorbent material in the oil vapour pressure-swing adsorption process.
Below will combine embodiment to specify embodiment of the present invention, how the utilisation technology means solve technical problem to the present invention whereby, and the implementation procedure of reaching technique effect can make much of and implement according to this.
The dewatering silica gel pore structure parameter is measured
ASAP2020M+C gas adsorption appearance with U.S. Micrometics company is measured N2 adsorption-desorption thermo-isopleth under 77K; Sample is at first 150 ℃ of temperature; Vacuum tightness 100mmHg is degassing 4h down; Adopt the specific surface area of BET method calculation sample, with the pore volume and the aperture of the calculating of BJH method, analytic sample, measuring result is seen table 1.
Water vapor adsorption measurement amount
In order to estimate the hydrophobization performance of silica gel; Analytical unit quality hydrophobic silicone is 30 ℃ of temperature; Humidity is the water vapor adsorption amount under the 80%Rh; It is higher that the less sorbent material of adsorptive capacity is evaluated as the hydrophobization performance, and used temperature and humidity conditions uses the PR-3G temperature and humidity regulator of Shanghai ESPEC company to provide.As auxiliary evaluation, sample is steeped in water, whether the back observation of 3 weeks breaks, and the result sees table 2.
The oil gas adsorptive capacity is measured
In order to estimate the adsorptive power of dewatering silica gel, in thermostatic vacuum drier, place a certain amount of No. 93 gasoline, to produce saturated oil steam to oil gas; The sub-sieve of the hydrophobic silicone that embodiment 1 to 8 preparation is housed is placed on adsorbed oil steam on the dividing plate, weighs, under the 2KPa vacuum condition, make the silica gel desorption then; Repeat 10 absorption/desorption circulations, draw hydrophobic silicone to the oil vapour equilibrium adsorption capacity, in order to compare; Identical hydrophobic silicone at 30 ℃, is placed after 2 days in the temperature and humidity regulator of humidity 80%Rh, carried out above absorption/desorption circulation; Obtain the oil gas adsorptive capacity of dewatering silica gel after the moisture absorption, the result sees table 2.
Embodiment 1
Present embodiment selects for use the Type B absorbent particle silica gel of Haiyang Chemical Plant, Qingdao's production as raw material, particle diameter 4mm, and specific surface area is 653.57m
2/ g, pore volume are 0.76cm
3/ g, mean pore size is 4.76nm.Get the raw material silica gel 500g is dried 2h in 120 ℃ of baking ovens after; Place there-necked flask, begin to stir behind the adding 800g trichloromethane, the properties-correcting agent trimethylchlorosilane is slowly splashed into; The mass ratio of trimethylchlorosilane and raw material silica gel is 1: 5; Connect the sour device of suction in the there-necked flask outlet, as acid-acceptor, under 30 ℃ of constant temperature, react 2h with water.Reaction finishes the back suction filtration, and with the drip washing several times of 600mL trichloromethane, again with 600mL exsiccant methyl alcohol and flushing of 40mL triethylamine and suction filtration, sample takes out and obtains hydrophobic silicone 90 ℃ of following vacuum-dryings 4 hours at last, and its pore structure parameter is seen table 1.
Embodiment 2
In the present embodiment; Identical among preparation hydrophobic silicone technology and the embodiment 1; The mass ratio of different is trimethylchlorosilane and silica gel dosage is 1: 10; In 30 ℃ of following reaction times of constant temperature is 3h, and the drip washing after reaction finishes is also identical with embodiment 1 with vacuum drying step, and the pore structure parameter of the hydrophobic silicone of processing is seen table 1.
Embodiment 3
Present embodiment selects for use the Type B absorbent particle silica gel of Haiyang Chemical Plant, Qingdao's production as raw material, particle diameter 4mm, and specific surface area is 653.57m
2/ g, pore volume are 0.76cm
3/ g, mean pore size is 4.76nm.Get the raw material silica gel 500g is dried 2h in 120 ℃ of baking ovens after; Place there-necked flask, begin to stir behind the adding 800g trichloromethane, properties-correcting agent trimethylammonium oxygen ethylsilane is slowly splashed into; The mass ratio of trimethylammonium oxygen ethylsilane and raw material silica gel is 1: 5, reaction 6h under 40 ℃ of constant temperature.Reaction finishes the back suction filtration, with the drip washing several times of 600mL trichloromethane, uses exsiccant washed with methanol and suction filtration at last again, and sample takes out and obtains hydrophobic silicone 90 ℃ of following vacuum-dryings 4 hours, and its pore structure parameter is seen table 1.
Embodiment 4
Present embodiment selects for use the Type B absorbent particle silica gel of Haiyang Chemical Plant, Qingdao's production as raw material, particle diameter 4mm, and specific surface area is 653.57m
2/ g, pore volume are 0.76cm
3/ g, mean pore size is 4.76nm.Get the raw material silica gel 500g is dried 2h in 120 ℃ of baking ovens after; Place there-necked flask, begin to stir behind the adding 800g trichloromethane, the properties-correcting agent diethyl dichlorosilane is slowly splashed into; The mass ratio of diethyl dichlorosilane and raw material silica gel is 1: 20; Connect to inhale sour device in the there-necked flask exit, with water as inhaling acid solution, at 40 ℃ of following isothermal reaction 2h.Reaction finishes the back suction filtration, and with the drip washing several times of 600mL trichloromethane, again with 600mL exsiccant methyl alcohol and flushing of 50mL triethylamine and suction filtration, sample takes out and obtains hydrophobic silicone 90 ℃ of following vacuum-dryings 4 hours at last, and its pore structure parameter is seen table 1.
Embodiment 5
Present embodiment selects for use the Type B absorbent particle silica gel of Haiyang Chemical Plant, Qingdao's production as raw material, particle diameter 4mm, and specific surface area is 653.57m
2/ g, pore volume are 0.76cm
3/ g, mean pore size is 4.76nm.Get the raw material silica gel 500g is dried 2h in 120 ℃ of baking ovens after; Place there-necked flask, begin to stir behind the adding 800g trichloromethane, the properties-correcting agent dichloromethyl phenylsilane is slowly splashed into; The mass ratio of dichloromethyl phenylsilane and raw material silica gel is 1: 20; Connect in there-necked flask outlet and to inhale sour device, with water as inhaling acid solution, at 40 ℃ of following isothermal reaction 4h.Reaction finishes the back suction filtration, and with the drip washing several times of 600mL trichloromethane, again with 600mL exsiccant methyl alcohol and flushing of 50mL triethylamine and suction filtration, sample takes out and obtains hydrophobic silicone 90 ℃ of following vacuum-dryings 4 hours at last, and its pore structure parameter is seen table 1.
Embodiment 6
Present embodiment selects for use the Type B absorbent particle silica gel of Haiyang Chemical Plant, Qingdao's production as raw material, particle diameter 4mm, and specific surface area is 653.57m
2/ g, pore volume are 0.76cm
3/ g, mean pore size is 4.76nm.Get 500g and in 120 ℃ of baking ovens, dry the raw material silica gel after 2 hours; Place there-necked flask; Begin to stir after adding the 800g trichloromethane, the properties-correcting agent diphenyl dichlorosilane is slowly splashed into, the mass ratio of diphenyl dichlorosilane and silica gel amount is 1: 5; The sour device of external suction on the there-necked flask, reaction is 2 hours under 30 ℃ of constant temperature.Reaction finishes the back suction filtration, and with the drip washing several times of 600mL trichloromethane, again with 600mL exsiccant methyl alcohol and flushing of 50mL triethylamine and suction filtration, sample takes out and obtains hydrophobic silicone 90 ℃ of following vacuum-dryings 4 hours at last, and its pore structure parameter is seen table 1.
Embodiment 7
Present embodiment selects for use the Type B absorbent particle silica gel of Haiyang Chemical Plant, Qingdao's production as raw material, particle diameter 4mm, and specific surface area is 653.57m
2/ g, pore volume are 0.76cm
3/ g, mean pore size is 4.76nm.Get 500g and in 120 ℃ of baking ovens, dry the raw material silica gel after 2 hours; Place there-necked flask, begin to stir behind the adding 800g trichloromethane, the properties-correcting agent hexamethyldisilazane is slowly splashed into; The mass ratio of hexamethyldisilazane and raw material silica gel is 1: 5, reaction 2h under 30 ℃ of constant temperature.Reaction finishes the back suction filtration, with the drip washing several times of 600mL trichloromethane, again with 600mL exsiccant methyl alcohol and flushing of 50mL triethylamine and suction filtration, takes out and obtains hydrophobic silicone at last, and its pore structure parameter is seen table 1.
Embodiment 8
Present embodiment selects for use the Type B absorbent particle silica gel of Haiyang Chemical Plant, Qingdao's production as raw material, particle diameter 4mm, and specific surface area is 653.57m
2/ g, pore volume are 0.76cm
3/ g, mean pore size is 4.76nm.Get 500g and in 120 ℃ of baking ovens, dry the raw material silica gel after 2 hours; Place there-necked flask; Begin to stir after adding a certain amount of trichloromethane, the properties-correcting agent dimethyldichlorosilane(DMCS) is slowly splashed into, the mol ratio of dimethyldichlorosilane(DMCS) and silica gel amount (in Si) is 1: 40; The sour device of external suction on the there-necked flask, reaction is 2 hours under 30 ℃ of constant temperature.Reaction finishes the back suction filtration, and with the drip washing several times of 600mL trichloromethane, again with 600mL exsiccant methyl alcohol and flushing of 50mL triethylamine and suction filtration, sample takes out and obtains finished product at 90 ℃ of following vacuum-drying 4h at last.Its pore structure parameter is seen table 1.
Comparative example 1
Present embodiment selects for use the A type absorbent particle silica gel of Haiyang Chemical Plant, Qingdao's production as raw material, and particle diameter is 5mm, and specific surface area is 680.29m
2/ g, pore volume are 0.51cm
3/ g, mean pore size is 3.02nm.Raw material silica gel is warmed up to 500 ℃ with the speed of 15 ℃/m, and under this temperature, kept 4 hours, be chilled to take out after the room temperature and obtain finished product, its physico-chemical property is seen table 1.
Comparative example 2
Present embodiment is that slowly to join the 300mL mass concentration be that stirring reaction generates the water-sol, in becoming the glue process in 20% the sodium silicate solution for the sulfuric acid of 0.5mol/L with the 300mL volumetric molar concentration; Add the 100mL mass concentration and be 2% CMC 99.5, stir and carry out ageing 24h, wash be neutrality to pH after; In hot air drier, dry 3h down for 120 ℃, after the taking-up, at 350 ℃ of following roasting 2h; Obtain finished product, its surface properties is seen table 1.
The pore structure parameter of table 1 dewatering silica gel
| Embodiment | Specific surface area | Pore volume | The aperture | The specific surface area decrement | Outward appearance |
| ?1 | 508.49 | 0.568 | 4.47 | 22.2％ | Spheroidal particle |
| ?2 | 545.59 | 0.620 | 4.54 | 16.5％ | Spheroidal particle |
| ?3 | 536.71 | 0.571 | 4.26 | 17.9％ | Spheroidal particle |
| ?4 | 568.60 | 0.648 | 4.56 | 13.0％ | Spheroidal particle |
| ?5 | 535.28 | 0.566 | 4.23 | 18.1％ | Spheroidal particle |
| ?6 | 507.50 | 0.627 | 4.37 | 22.3％ | Spheroidal particle |
| ?7 | 545.45 | 0.627 | 4.59 | 16.5％ | Spheroidal particle |
| ?8 | 572.65 | 0.661 | 4.62 | 12.4％ | Spheroidal particle |
| Comparative example 1 | 391.44 | 0.559 | 5.74 | 73.8％ | Spheroidal particle |
| Comparative example 2 | 423.72 | 0.302 | 2.27 | ?-- | Powdered |
Table 2 dewatering silica gel hydrophobicity and oil gas absorption property
Can know from the result of table 1 and table 2, adopt the hydrophobic silicone of preparing method's preparation of the present invention, the formed form of spherical particles that is shaped as; Be not easy after soaked to break; Be not easy to take place problems such as vacuum pump body obstruction, be applicable to pressure swing adsorption technique, and adopt the soaked back of silica gel of preparing method's preparation of comparative example 1 to break easily; And specific surface area reduces more; The method of employing comparative example 2 is Powdered through the hydrophobic silicone of acid and water glass prepared in reaction, problems such as vacuum pump body obstruction all takes place easily, inapplicable pressure swing adsorption technique when in pressure swing adsorption technique, using.And the oil gas adsorptive capacity result after water vapor adsorption amount result and moisture absorption finds out; Adopt the hydrophobicity of hydrophobic silicone of preparation method of the present invention preparation better; When water vapour exists; Its oil gas adsorptive capacity changes very little, explains that its selection adsorptive power to oil gas is stronger, and these characteristics explain that also this dewatering silica gel more is applicable to the absorbing process that oil gas reclaims.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any professional and technical personnel of being familiar with possibly utilize the technology contents of above-mentioned announcement to change or be modified as the equivalent embodiment of equivalent variations.But everyly do not break away from technical scheme content of the present invention,, still belong to the protection domain of technical scheme of the present invention according to any simple modification, equivalent variations and the remodeling that technical spirit of the present invention is done above instance.
All are above-mentioned to be the primary device for carrying out said of this intellecture property, does not set restriction and implements this new device and detection method and/or working method with other form.Those skilled in the art will utilize this important information, foregoing revised, to realize similar implementation status.But all are based on modification of the present invention or transform novel method, belong to the right of reservation.
Claims (10)
1. one kind is used for the hydrophobic silicone that oil gas reclaims, and it is characterized in that the preparation method of said silica gel comprises the steps:
The first step, with the water-absorbent silica gel particle as raw material silica gel particle, at high temperature heating, drying;
Second step, the said raw material silica gel after the oven dry is mixed with pre-dry organic solvent, add surface-modifying agent, stirring reaction;
In the 3rd step, after the second step stirring reaction finishes, reaction product is carried out suction filtration, and repeatedly wash with the exsiccant solvent;
In the 4th step, through the reaction product after the flushing, obtain said hydrophobic silicone in dry the 3rd step;
Prepared hydrophobic silicone be shaped as form of spherical particles.
2. hydrophobic silicone as claimed in claim 1, it is characterized in that: the particle diameter of the hydrophobic silicone that is finally made is preferably 4-6mm, and specific surface area is preferably 350-880m
2/ g, the aperture is preferably 4nm-10nm, and with respect to the hydrophobic silicone solid particulate, the water vapor adsorption amount of the said hydrophobic silicone that finally makes is preferably 0.03-0.45g/g.
3. according to claim 1 or claim 2 hydrophobic silicone, it is characterized in that: Heating temperature is preferably about 2-9 hour said heat-up time for about 150 ℃ of about 115-in the said the first step.
4. like the described hydrophobic silicone of claim 1 to 3, it is characterized in that: the time of stirring reaction is preferably about 2-11 hour in said second step, and the temperature of stirring reaction is about 20 ℃-50 ℃, and the said surface-modifying agent that adds in said second step can general formula be R
aH
bSiX
4-a-bIn the represented compound one or more mix, and wherein R is selected from alkyl that comprises 1 to 12 carbon atom and the substituted alkyl of organo-functional group that comprises 1 to 12 carbon atom, and said alkyl is selected from saturated alkane base, alkylene, aryl, cycloalkyl group; Said organo-functional group is selected from saturated alkane base, alkylene, aryl, cycloalkyl group, amino etc., and X is selected from halogen and the alkoxyl group that comprises 1 to 12 carbon atom, a=0,1,2 or 3; B=0 or 1; A+b=1,2 or 3, when b=1, a+b=2 or 3; With respect to said raw material silica gel particulate amount, the add-on of said surface-modifying agent is 0.5wt%-20wt%.
5. like the described hydrophobic silicone of claim 1 to 4; It is characterized in that: the exsiccant solvent in said the 3rd step is organic solvent and/or alcoholic solvent through processed; The adjusting that has also added organic bases promotion pH value in said the 3rd step; In said the 4th step, the exsiccant temperature is about 150 ℃ of about 60-, and the exsiccant time is about 2-4 hour.
6. one kind is used for the hydrophobic silicone that oil gas reclaims, and it is characterized in that the preparation method of said hydrophobic silicone comprises the steps:
The first step, with the water-absorbent silica gel particle as raw material silica gel particle, at high temperature heating, drying;
Second step, the said raw material silica gel after the oven dry is mixed with pre-dry organic solvent, slowly add surface-modifying agent, stirring reaction;
In the 3rd step, after the second step stirring reaction finishes, reaction product is carried out suction filtration, and repeatedly wash with the exsiccant solvent;
In the 4th step, through the reaction product after the flushing, obtain said hydrophobic silicone in dry the 3rd step;
Said raw material silica gel particle grain size is 3-6mm, and specific surface area is 450-700m
2/ g, the aperture is 3nm-7nm, pore volume is 0.38-0.90cm
3/ g;
The temperature of the heating in the said the first step is 115 ℃-130 ℃, and the time of heating is 2-4 hour;
The time of stirring reaction is 2-4 hour in said second step, and the temperature of stirring reaction is 20 ℃-50 ℃, and stirring reaction carries out under constant temperature;
The exsiccant temperature is 60 ℃-150 ℃ in said the 4th step, and the exsiccant time is 2-4 hour;
With respect to said raw material silica gel particulate amount, the add-on of surface-modifying agent is 0.5wt%-20wt% described in said second step;
With respect to the add-on of said surface-modifying agent, the add-on of organic bases is 25wt%-60wt% described in the 3rd step;
The hydrophobic silicone that is finally made be shaped as form of spherical particles;
The particle diameter of the hydrophobic silicone that is finally made is preferably 4-6mm, and specific surface area is preferably 500-730m
2/ g, the aperture is preferably 4nm-7nm, and pore volume is 0.55-0.70cm
3/ g, with respect to the hydrophobic silicone solid particulate, the water vapor adsorption amount of the said hydrophobic silicone that finally makes is preferably 0.03-0.45g/g.
7. sorbent material is characterized in that: the mixture that said sorbent material is is staple by each described hydrophobic silicone of claim 1 to 6, mixture divide two-layer layout up and down, and the upper strata is that specific surface area is at 900-1500m
2/ g scope, pore size distribution be in the granular adsorption agent of 2-4nm scope, preferred columnar activated carbon, and lower floor is a hydrophobic silicone.
8. sorbent material as claimed in claim 7 is characterized in that: with respect to the solid weight of said sorbent material, the content of said hydrophobic silicone is preferably 30%-70%, and most preferred content is 40%-60%.
9. each hydrophobic silicone or claim 7 or the 8 described sorbent materials application at least one process of production, transportation and storage of petroleum products in the claim 1 to 6.
10. each hydrophobic silicone or claim 7 or 8 application of described sorbent material in the pressure-swing adsorption process of oil vapour in the claim 1 to 6.
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| CN102757058A (en) * | 2012-06-12 | 2012-10-31 | 山东辛化硅胶有限公司 | Novel B type large-pore volume silica gel and manufacture method thereof |
| CN102974322A (en) * | 2012-10-31 | 2013-03-20 | 浙江工业大学 | Hydrophobic silica gel composite resin-based VOC adsorbent |
| CN108939867A (en) * | 2017-05-24 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of administering method of volatility sulfur-containing organic waste gas |
| CN113876989A (en) * | 2021-10-09 | 2022-01-04 | 苏州同构科技有限公司 | Diatomite deodorant and application thereof |
| CN114247418A (en) * | 2021-12-22 | 2022-03-29 | 苏州东杏新材料科技有限公司 | Hydrophobic and oleophobic modified silica gel adsorbent and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757058A (en) * | 2012-06-12 | 2012-10-31 | 山东辛化硅胶有限公司 | Novel B type large-pore volume silica gel and manufacture method thereof |
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| CN102974322A (en) * | 2012-10-31 | 2013-03-20 | 浙江工业大学 | Hydrophobic silica gel composite resin-based VOC adsorbent |
| CN102974322B (en) * | 2012-10-31 | 2014-12-03 | 浙江工业大学 | Hydrophobic silica gel composite resin-based VOC adsorbent |
| CN108939867A (en) * | 2017-05-24 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of administering method of volatility sulfur-containing organic waste gas |
| CN113876989A (en) * | 2021-10-09 | 2022-01-04 | 苏州同构科技有限公司 | Diatomite deodorant and application thereof |
| CN114247418A (en) * | 2021-12-22 | 2022-03-29 | 苏州东杏新材料科技有限公司 | Hydrophobic and oleophobic modified silica gel adsorbent and preparation method thereof |
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