CN103599814B - A kind of high temperature resistant preparation with the superpower solid acid of the asphaltic base of hydrolysis - Google Patents
A kind of high temperature resistant preparation with the superpower solid acid of the asphaltic base of hydrolysis Download PDFInfo
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- 239000011973 solid acid Substances 0.000 title claims abstract description 52
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 32
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 29
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000967 suction filtration Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 230000031709 bromination Effects 0.000 claims abstract description 16
- 238000005893 bromination reaction Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000005864 Sulphur Substances 0.000 claims abstract description 10
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000004044 response Effects 0.000 claims description 13
- 238000006277 sulfonation reaction Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 8
- 239000011300 coal pitch Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 4
- WZUQMOGWPIRDHH-UHFFFAOYSA-N butyl 2-methyl-3-oxobutanoate Chemical compound CCCCOC(=O)C(C)C(C)=O WZUQMOGWPIRDHH-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- -1 acetyl butyl Chemical group 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009229 glucose formation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A high temperature resistant preparation with the superpower solid acid of the asphaltic base of hydrolysis is carbonized coal tar pitch nitrogen protection at a certain temperature; After mix in proportion with sulphur again, sulfuration is carried out in nitrogen protection at a certain temperature; Then add dimethylbenzene, bromine water and, hydrogen peroxide reacts, then neutralizes, and through suction filtration, washing and drying, obtains bromination coal tar pitch; Finally in bromination coal tar pitch, add dimethylbenzene and the concentrated sulfuric acid again, through suction filtration, washing and drying, the obtained superpower solid acid of asphaltic base.Prepared superpower solid acid has higher thermal stable temperature and hydrolysis temperature, overcome and reusing at first solid acid catalyst the drawback reducing catalytic activity in process owing to there is hydrolysis, expand the scope of application of solid acid, improve the industrial application value of solid acid, have broad application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of coal tar pitch solid acid, take especially coal tar pitch as raw material, by carbonizing coal tar pitch, sulfuration, bromination and sulfonation process the preparation method of a kind of high temperature resistant and superpower solid acid of the asphaltic base of hydrolysis.
Technical background
Many reactions just can be carried out under acid catalyst effect as esterification, isomerization and alkylation etc. all need, although as catalyst, liquid acid has that price is low, excellent catalytic effect and the advantage such as applied widely, but exist consersion unit seriously corroded, and change that and repair apparatus needs to stop production and be difficult to reactant and product to be separated, not easily reclaims and waste liquid has a strong impact on the shortcomings such as environment.Thus the acid catalyst of development of new, seeks green cleaner production and zero release of pollutant is the emphasis that countries in the world are studied.In view of solid acid also has acid catalyzed effect; but it is very little to consersion unit corrosivity; and recyclablely to use again; greatly can reduce production cost; also the feature of protection of the environment is conducive to; this kind of material has broad application prospects at catalytic field, thus becomes the Main way developing following acid catalyst.Existing superpower solid acid has the catalytic effect same with liquid acid as catalyst, but less to equipment corrosion, environmentally safe, and the recyclable advantage such as to use again, be the main development direction of following acid catalyst.In all types of superpower solid acids, as in zeolite molecular sieve, ion exchange resin, heteropoly acid etc., be especially more popular with carbon-based solid acid.Because carrier carbon has the feature of resistance to strong acid and resistance to highly basic, not easily react with other component of reaction system and produce interference etc.In published document, many carbonaceous materials such as wood chip, maize straw, starch, cotton etc. all can be applied in different reaction systems as the raw material preparing the superpower solid acid of carbon back, but the subject matter existed is that Surface acidity is low, be generally 3.0-3.5mmol/g, active component loses catalytic action because of facile hydrolysis (140 DEG C are just hydrolyzed), catalytic effect is poor, and poor heat stability (softening point temperature 186 DEG C).See " chemistry of forest product and industry ", 2013,33(2) report use
/ SnO
2solid acid is that catalyst is to catalysis conversion of glucose synthesis of acetyl butyl propionate in butanols system, when catalyst reuses 5 times at 200 DEG C of temperature, the 1st, the 2nd, the 3rd, the 4th, the 5th use after the yield of Butyl acetylpropanoate be respectively 19.5 %, 20.6 %, 17.9 %, 15.4 %, 12.8 %, namely along with the increase of access times, catalytic capability is reducing gradually, and catalyst exists serious hydrolysis phenomena.
Existing CN102716767A discloses " a kind of preparation method of peracid amount carbon-based solid acid ".This invention adopts coal tar pitch to be raw material, made superpower solid acid, Surface acidity is no doubt very high, but exists when temperature, higher than 140 DEG C, hydrolysis to a certain degree occurs later, and start to occur to soften at 186 DEG C, cause catalyst to be after completion of the reaction not easy the problem reclaimed.In addition, for the reaction at high temperature just can carried out, this catalyst can not meet this kind of reaction requirement because of hydrolysis and thermally-stabilised difference.
Therefore, improve hydrolysis occurs catalyst temperature and heat endurance, be satisfy the demand acid catalysis and at relatively high temperatures reaction could there is the problem that must solve, and the range of application of further expansion solid acid.
Summary of the invention
Problem of the present invention is to improve solid acid catalyst generation hydrolysising reacting temperature and heat endurance, and provides a kind of high temperature resistant preparation method with the superpower solid acid of the asphaltic base of hydrolysis.
Based on the problems referred to above and object, the measure that the present invention takes is as follows:
A high temperature resistant preparation with the superpower solid acid of the asphaltic base of hydrolysis, the technology path of employing is the charing of coal tar pitch, sulfuration, bromination and sulfonation, and its concrete preparation method is as follows:
Be 700 ~ 900 DEG C by coal tar pitch in temperature, nitrogen protection air-flow is under 70 ~ 100ml/min, charing 4 ~ 6h;
Be that the ratio of 4:1 mixes with mass ratio by coal tar pitch and the sulphur after charing, temperature be 260 ~ 360 DEG C, under nitrogen flow rate is the condition of 70 ~ 100ml/min, sulfuration 1 ~ 4h;
After coal tar pitch after sulfuration is cooled to 30 ~ 50 DEG C, stop logical nitrogen, insert in the reactor with reflux condensate device again, add volume by the coal tar pitch after every gram of sulfuration and be respectively the dimethylbenzene of 5ml, 7.5ml and 7.5ml or toluene, bromine water and mass concentration are the hydrogen peroxide of 30%, then under temperature is 140 ~ 160 DEG C of conditions, reaction 8 ~ 10h, after question response terminates, add the sodium hydroxide solution that mass concentration is 10% again, be neutralized to neutrality, through suction filtration, distilled water washing and drying, obtain bromination coal tar pitch;
Bromination coal tar pitch is added volume by every gram, and to be respectively the dimethylbenzene of 10ml or toluene and 5 ~ 8ml, mass concentration be the concentrated sulfuric acid of 98%, under temperature is 170 DEG C of conditions, reaction 10 ~ 14h, through suction filtration, distilled water washing and drying after reaction terminates, obtained a kind of high temperature resistant solid acid superpower with the asphaltic base of hydrolysis.
In technique scheme, described coal tar pitch is medium temperature coal pitch or coal tar pitch; Described high temperature resistant be 290 DEG C with the softening point of the superpower solid acid of the asphaltic base of hydrolysis, Surface acidity is 6.8 mmol/L, is not hydrolyzed below 220 DEG C of temperature.
Implement the preparation method of the above-mentioned described a kind of high temperature resistant and superpower solid acid of the asphaltic base of hydrolysis of the present invention, after the charing to coal tar pitch appropriateness, further vulcanization crosslinking, improves the degree of polymerization that coal tar pitch does not carbonize component completely, increases stability on the one hand; On the other hand, in matrix, introduce sulphur atom, the acid application point of the oxidized generation of sulphur in subsequent oxidation process.Under the existence of oxidants hydrogen peroxide and bromine, with not carbonizing component generation substitution reaction completely thus being introduced in skeleton, the bromine atoms of introducing can electron cloud on passivation hydrocarbon molecules skeleton, is convenient to introduce sulfonic acid group, improves acid amount through oversulfonate.In addition, owing to there being the existence of deactivating group bromine atoms, not easily being there is the hydroxyl radical attacks of nucleophilic character, thus effectively prevented the hydrolysis of solid acid.
By technique scheme, coal tar pitch is processed, obtained superpower solid acid both ensure that the quantity of acid amount, turn improve thermal stable temperature and hydrolysis temperature, hydrolysis temperature occurs and brings up to 220 DEG C by original 140 DEG C, softening point has brought up to 290 DEG C by 186 DEG C.Using the catalyst that prepared solid acid is Butyl acetylpropanoate as catalysis conversion of glucose in butanols system, at 200 DEG C of temperature reusable 6 times, the yield of Butyl acetylpropanoate all remains on 17.8 ~ 19.5%, overcomes previous use
/ SnO
2solid acid is catalyst, and reusing the drawback reducing catalytic activity in process owing to there is hydrolysis, catalyst recovery yield is up to 98%.The temperature that the made superpower solid acid hydrolysis of the method disclosed in the made solid acid of this method and CN102716767A that gives in Figure of description 1 occurs compares.Therefrom be very easy to find, the temperature that hydrolysis occurs the present invention's made solid acid is improved significantly.
Adopt superpower solid acid prepared by the inventive method, the catalyst that reacts can be carried out under 30 ~ 220 DEG C of higher temperatures as various acid catalysis, effectively expand the scope of application of this solid acid, improve industrial application value, due to the character of uniqueness, broad prospect of application will be had in acid catalyzed reaction system.
Detailed description of the invention
Below the specific embodiment of the present invention is further illustrated.
Superpower solid acid softening point prepared by existing coal tar pitch is low, easy generation is softening and be hydrolyzed and lose catalytic activity, and then affect its result of use, the present invention adopts the superpower solid acid prepared by a kind of high temperature resistant preparation method with the superpower solid acid of the asphaltic base of hydrolysis to overcome above-mentioned defect, the technology path adopted is: coal tar pitch charing-sulfuration-bromination-sulfonation, concrete preparation method is by coal tar pitch first temperature 700 ~ 900 DEG C, N
2shielding gas flow is carbonize 4 ~ 6h under 70 ~ 100ml/min; Mix by the mode that coal tar pitch and the sulphur after charing take mass ratio as 4:1 again, temperature be 260 ~ 360 DEG C, nitrogen flow rate be 70 ~ 100ml/min condition under sulfuration 1 ~ 4h; Then 30 ~ 50 DEG C are cooled to, stop logical nitrogen, and the product after sulfuration is added in the reactor with reflux condensate device, add volume by every gram of sulfur product and be respectively the dimethylbenzene of 5ml, 7.5ml and 7.5ml or toluene, bromine water and mass concentration are the hydrogen peroxide of 30%, then under temperature is 140 ~ 160 DEG C of conditions react 8 ~ 10h, after question response terminates, add mass concentration be 10% sodium hydroxide solution be neutralized to neutrality, through suction filtration, distilled water washing and drying, obtain brominated product;
And then adding volume in the product of every gram of bromination, to be respectively the dimethylbenzene of 10ml or toluene and 5 ~ 8ml, mass concentration be the concentrated sulfuric acid of 98%, 10 ~ 14h is reacted under temperature is 170 DEG C of conditions, through suction filtration, distilled water washing and drying after reaction terminates, prepare a kind of softening point and reach 290 DEG C, be not hydrolyzed below 220 DEG C of temperature, acid amount reaches the superpower solid acid of 6.8 mmol/L.Raw materials used coal tar pitch is not by the restriction of pitch kind, and can be medium temperature coal pitch, also can be coal tar pitch; Also the restriction of coal tar pitch is not produced by the place of production and process conditions.
Implementing the present invention's a kind of high temperature resistant and preparation that the is superpower solid acid of asphaltic base that is hydrolysis described above is by carbonizing coal tar pitch, then sulfuration.By sulfuration, improve the degree of cross linking between aromatic ring on the one hand, and then improve the heat endurance of material, in the material of charing, introduce a certain amount of sulphur atom on the other hand, increased the acid active site position of material by later stage chemical oxidation; Then bromination, to introducing more bromine atoms in the benzene ring structure of graphene sheet layer, and by sulfonation to increase the active acid position of carbon based surfaces, improving acid strength, strengthening acid catalysis ability.The superpower solid acid that the present invention obtains, the temperature that hydrolysis occurs has brought up to 220 DEG C by 110 DEG C (comparing with without the superpower solid acid of the made asphaltic base of the art of this patent route); Softening point has brought up to 290 DEG C by 186 DEG C, and its acid amount can reach 6.8mmol/g, is 2 times of conventional solid acid acid amount.Made superpower solid acid can meet the required catalysts conditions that just can react at relatively high temperatures, has greatly expanded the solid acid scope of application.Raw materials used coal tar pitch abundance, low price, institute's controlling catalyst to the reaction of glucose catalyzed conversion Butyl acetylpropanoate after reusing 10 times, conversion ratio is constant, be more than 18.6%, effect is equal to liquid acid, illustrates that catalyst has excellent catalytic action and stability.
Below by specific embodiment, the specific embodiment of the present invention is made an explanation.
Embodiment 1
50g coal tar pitch is placed in tube furnace, at N
2flow is 70ml/min, carbonize 5h under temperature 750 DEG C of conditions, then the mode of the coal tar pitch after charing and sulphur 4:1 is in mass ratio mixed to be placed on tube furnace and to carry out sulfuration, still uses N
2protection, flow is 70ml/min, under temperature 260 DEG C of conditions, react 2h, stops logical nitrogen after being cooled to 30 DEG C; Product after sulfuration is added in the reactor with reflux condensate device, the hydrogen peroxide that dimethylbenzene, bromine water and mass concentration are 30% is added by the product after every gram of sulfuration, its volume is respectively 5ml, 7.5ml and 7.5ml, then under temperature is 160 DEG C of conditions, 10h is reacted, after question response terminates, add mass concentration be 10% sodium hydroxide solution carry out being neutralized to neutrality, through suction filtration, distilled water washing and dry, obtain brominated product; Product after bromination needs to carry out sulfonation.Namely in every gram of brominated product, dimethylbenzene is added and mass concentration is the concentrated sulfuric acid of 98%, volume is respectively 8ml and 10ml, 14h is reacted under temperature is 170 DEG C of conditions, through suction filtration, distilled water washing and drying after question response terminates, obtain sour amount and can reach 6.9mmol/l, softening point 290 DEG C, hydrolysis temperature reach the superpower solid acid of 220 DEG C.
Embodiment 2
50g coal tar pitch is placed in tube furnace, at N
2flow is 80ml/min, carbonize 1h under temperature 900 DEG C of conditions, then the mode of the coal tar pitch after charing and sulphur 4:1 is in mass ratio mixed to be placed on tube furnace and to carry out sulfuration, uses N
2protection, flow is 90ml/min, under temperature 360 DEG C of conditions, react 4h, stops logical nitrogen after being cooled to 50 DEG C; Product after sulfuration is added in the reactor with reflux condensate device, the hydrogen peroxide that toluene, bromine water and mass concentration are 30% is added by the product after every gram of sulfuration, its volume is respectively 5ml, 7.5ml and 7.5ml, then under temperature is 140 DEG C of conditions, 8h is reacted, after question response terminates, add mass concentration be 10% sodium hydroxide solution carry out being neutralized to neutrality, through suction filtration, distilled water washing and dry, obtain brominated product; Product after bromination needs to carry out sulfonation.Namely in every gram of brominated product, toluene is added and mass concentration is the concentrated sulfuric acid of 98%, volume is respectively 8ml and 10ml, 10h is reacted under temperature is 170 DEG C of conditions, through suction filtration, distilled water washing and drying after question response terminates, obtain sour amount and can reach 6.5mmol/l, softening point 290 DEG C, hydrolysis temperature reach the superpower solid acid of 220 DEG C.
Embodiment 3
50g coal tar pitch is placed in tube furnace, at N
2flow is 100ml/min, carbonize 3h under temperature 850 DEG C of conditions, then the mode of the coal tar pitch after charing and sulphur 4:1 is in mass ratio mixed to be placed on tube furnace and to carry out sulfuration, uses N
2protection, flow is 80ml/min, under temperature 320 DEG C of conditions, react 1h, stops logical nitrogen after being cooled to 40 DEG C; Product after sulfuration is added in the reactor with reflux condensate device, the hydrogen peroxide that dimethylbenzene, bromine water and mass concentration are 30% is added by the product after every gram of sulfuration, its volume is respectively 5ml, 7.5ml and 7.5ml, then under temperature is 150 DEG C of conditions, 9h is reacted, after question response terminates, add mass concentration be 10% sodium hydroxide solution carry out being neutralized to neutrality, through suction filtration, distilled water washing and dry, obtain brominated product; Product after bromination needs to carry out sulfonation.Namely in every gram of brominated product, dimethylbenzene is added and mass concentration is the concentrated sulfuric acid of 98%, volume is respectively 8ml and 10ml, 12h is reacted under temperature is 170 DEG C of conditions, through suction filtration, distilled water washing and drying after question response terminates, obtain sour amount and can reach 6.6mmol/l, softening point 290 DEG C, hydrolysis temperature reach the superpower solid acid of 218 DEG C.
Embodiment 4
50g coal tar pitch is placed in tube furnace, at N
2flow is 80ml/min, carbonize 5h under temperature 700 DEG C of conditions, then the mode of the coal tar pitch after charing and sulphur 4:1 is in mass ratio mixed to be placed on tube furnace and to carry out sulfuration, uses N
2protection, flow is 85ml/min, under temperature 300 DEG C of conditions, react 2.5h, stops logical nitrogen after being cooled to 40 DEG C; Product after sulfuration is added in the reactor with reflux condensate device, the hydrogen peroxide that toluene, bromine water and mass concentration are 30% is added by the product after every gram of sulfuration, its volume is respectively 5ml, 7.5ml and 7.5ml, then under temperature is 140 DEG C of conditions, 8h is reacted, after question response terminates, add mass concentration be 10% sodium hydroxide solution carry out being neutralized to neutrality, through suction filtration, distilled water washing and dry, obtain brominated product; Product after bromination needs to carry out sulfonation.Namely in every gram of brominated product, toluene is added and mass concentration is the concentrated sulfuric acid of 98%, volume is respectively 8ml and 10ml, 13h is reacted under temperature is 170 DEG C of conditions, through suction filtration, distilled water washing and drying after question response terminates, obtain sour amount and can reach 6.9mmol/l, softening point 280 DEG C, hydrolysis temperature reach the superpower solid acid of 220 DEG C.
Embodiment 5
50g coal tar pitch is placed in tube furnace, at N
2flow is 90ml/min, carbonize 3h under temperature 800 DEG C of conditions, then the mode of the coal tar pitch after charing and sulphur 4:1 is in mass ratio mixed to be placed on tube furnace and to carry out sulfuration, uses N
2protection, flow is 80ml/min, under temperature 350 DEG C of conditions, react 3h, stops logical nitrogen after being cooled to 30 DEG C; Product after sulfuration is added in the reactor with reflux condensate device, the hydrogen peroxide that dimethylbenzene, bromine water and mass concentration are 30% is added by the product after every gram of sulfuration, its volume is respectively 5ml, 7.5ml and 7.5ml, then under temperature is 150 DEG C of conditions, 9h is reacted, after question response terminates, add mass concentration be 10% sodium hydroxide solution carry out being neutralized to neutrality, through suction filtration, distilled water washing and dry, obtain brominated product; Product after bromination needs to carry out sulfonation.Namely in every gram of brominated product, dimethylbenzene is added and mass concentration is the concentrated sulfuric acid of 98%, volume is respectively 8ml and 10ml, 10h is reacted under temperature is 170 DEG C of conditions, through suction filtration, distilled water washing and drying after question response terminates, obtain sour amount and can reach 6.5mmol/l, softening point 290 DEG C, hydrolysis temperature reach the superpower solid acid of 215 DEG C.
Claims (2)
1. a high temperature resistant preparation method with the superpower solid acid of the asphaltic base of hydrolysis, the technology path of employing is charing to coal tar pitch, sulfuration, bromination and sulfonation, and its concrete preparation method is as follows:
Be 700 ~ 900 DEG C by coal tar pitch in temperature, nitrogen protection air-flow is under 70 ~ 100ml/min, charing 4 ~ 6h;
Be that the ratio of 4:1 mixes with mass ratio by coal tar pitch and the sulphur after charing, temperature be 260 ~ 360 DEG C, under nitrogen flow rate is the condition of 70 ~ 100ml/min, sulfuration 1 ~ 4h;
After coal tar pitch after sulfuration is cooled to 30 ~ 50 DEG C, stop logical nitrogen, insert in the reactor with reflux condensate device again, add volume by the coal tar pitch after every gram of sulfuration and be respectively the dimethylbenzene of 5ml, 7.5ml and 7.5ml or toluene, bromine water and mass concentration are the hydrogen peroxide of 30%, then under temperature is 140 ~ 160 DEG C of conditions, reaction 8 ~ 10h, after question response terminates, add the sodium hydroxide solution that mass concentration is 10% again, be neutralized to neutrality, through suction filtration, distilled water washing and drying, obtain bromination coal tar pitch;
Bromination coal tar pitch is added volume by every gram, and to be respectively the dimethylbenzene of 10ml or toluene and 5 ~ 8ml, mass concentration be the concentrated sulfuric acid of 98%, under temperature is 170 DEG C of conditions, reaction 10 ~ 14h, through suction filtration, distilled water washing and drying after reaction terminates, obtained a kind of high temperature resistant solid acid superpower with the asphaltic base of hydrolysis;
Described obtained a kind of high temperature resistant be 290 DEG C with the superpower solid acid softening point of the asphaltic base of hydrolysis, Surface acidity is 6.8 mmol/L, is not hydrolyzed below 220 DEG C of temperature.
2. preparation method as claimed in claim 1, coal tar pitch described in it is medium temperature coal pitch or coal tar pitch.
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| KR100896428B1 (en) * | 2007-11-12 | 2009-05-12 | 한국에너지기술연구원 | Production method of solid acid catalyst from spent oil shale for catalytic cracking of polymeric materials and heavy oil and production method of light oil using thereof |
| CN102716767A (en) * | 2012-07-04 | 2012-10-10 | 太原理工大学 | Preparation method of high-acid-content carbon-based solid acid |
| CN103263935A (en) * | 2013-06-08 | 2013-08-28 | 宁夏大学 | Preparation method and application of magnetic core-shell carbon-based solid acid |
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| KR100896428B1 (en) * | 2007-11-12 | 2009-05-12 | 한국에너지기술연구원 | Production method of solid acid catalyst from spent oil shale for catalytic cracking of polymeric materials and heavy oil and production method of light oil using thereof |
| CN102716767A (en) * | 2012-07-04 | 2012-10-10 | 太原理工大学 | Preparation method of high-acid-content carbon-based solid acid |
| CN103263935A (en) * | 2013-06-08 | 2013-08-28 | 宁夏大学 | Preparation method and application of magnetic core-shell carbon-based solid acid |
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