CN111298837A - Preparation method of modified solid acid catalyst with hydrocarbon resin as carrier - Google Patents
Preparation method of modified solid acid catalyst with hydrocarbon resin as carrier Download PDFInfo
- Publication number
- CN111298837A CN111298837A CN202010181447.9A CN202010181447A CN111298837A CN 111298837 A CN111298837 A CN 111298837A CN 202010181447 A CN202010181447 A CN 202010181447A CN 111298837 A CN111298837 A CN 111298837A
- Authority
- CN
- China
- Prior art keywords
- solution
- acid catalyst
- solid acid
- hydrocarbon resin
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011973 solid acid Substances 0.000 title claims abstract description 81
- 239000013032 Hydrocarbon resin Substances 0.000 title claims abstract description 69
- 229920006270 hydrocarbon resin Polymers 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 102
- 239000007822 coupling agent Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 41
- 229920012287 polyphenylene sulfone Polymers 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 230000003213 activating effect Effects 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 31
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910001863 barium hydroxide Inorganic materials 0.000 claims abstract description 19
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 238000001291 vacuum drying Methods 0.000 claims abstract description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000007865 diluting Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 118
- 239000000463 material Substances 0.000 claims description 51
- 230000001105 regulatory effect Effects 0.000 claims description 46
- 235000021355 Stearic acid Nutrition 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 150000004645 aluminates Chemical class 0.000 claims description 13
- 230000001276 controlling effect Effects 0.000 claims description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 13
- 239000008117 stearic acid Substances 0.000 claims description 13
- 239000012190 activator Substances 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 239000000395 magnesium oxide Substances 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/05—Stirrers
- B01F27/11—Stirrers characterised by the configuration of the stirrers
- B01F27/19—Stirrers with two or more mixing elements mounted in sequence on the same axis
- B01F27/191—Stirrers with two or more mixing elements mounted in sequence on the same axis with similar elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F31/00—Mixers with shaking, oscillating, or vibrating mechanisms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier comprises the steps of modifying and activating the hydrocarbon resin, stirring and mixing polyolefin resin and polyphenylene sulfone resin, dissolving the mixture by absolute ethyl alcohol, then adding calcium sulfate, silicon dioxide, an activating agent and a coupling agent, uniformly mixing, reacting at high temperature and drying to obtain modified and activated hydrocarbon resin; preparing solid acid catalyst precursor from AlCl3Solution and Na2SiO3Uniformly mixing the solution, adding a barium hydroxide solution and an ammonium chloride solution, and carrying out an ion exchange reaction to obtain a solid acid catalyst precursor; loading modified hydrocarbon resin on solid acid catalyst, pulverizing the modified activated hydrocarbon resin, and sievingThen carrying out vacuum drying, finally adding the solid acid catalyst precursor, diluting with absolute ethyl alcohol, carrying out suction filtration, washing and vacuum drying to obtain the modified solid acid catalyst taking hydrocarbon resin as a carrier; the method has mild reaction conditions, is simple and easy to operate, and is suitable for large-scale popularization.
Description
Technical Field
The invention relates to the technical field of solid acid catalysts, in particular to a preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier.
Background
The solid acid catalyst is an important catalyst in acid-base catalysts, and the catalytic function is derived from an acid site with catalytic activity on the surface of a solid, namely an acid center. Most of them are oxides or mixed oxides of non-transition elements, and their catalytic performance is different from that of oxide catalysts containing transition elements. These catalysts are widely used in catalytic reactions of ionic type mechanism, and are of many kinds. In addition, there are supported solid acid catalysts, which are formed by supporting a liquid acid on a solid carrier, such as a solid phosphoric acid catalyst. In recent years, the research of solid acid catalysts in biomass conversion has attracted much attention from domestic and foreign research. The solid acid catalyst can be well separated from the reaction liquid after the catalysis is finished, so that the subsequent reaction liquid treatment process is simplified, the treatment requirement is reduced, and the technical feasibility is realized.
However, in the preparation process of the existing solid acid catalyst, the process is complex, and the equipment volume is huge, so that the capital investment is large; on the other hand, the existing solid acid catalyst has low catalytic activity and poor stability.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a modified solid acid catalyst which has reasonable preparation process, high catalyst activity and high stability and takes hydrocarbon resin as a carrier.
The technical scheme of the invention is as follows: a preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier comprises the following steps:
s1, modifying and activating hydrocarbon resin;
s11, respectively weighing the following raw materials in parts by weight: 35-50 parts of polyolefin resin, 10-15 parts of polyphenylene sulfone resin, 5-8 parts of calcium sulfate, 3-5 parts of silicon dioxide, 0.8-1.2 parts of activating agent and 0.5-1 part of coupling agent;
s12, fully stirring and mixing the polyolefin resin and the polyphenylene sulfone resin weighed in the step S11 to form a mixed material, and uniformly mixing the mixed material and absolute ethyl alcohol according to the volume ratio of 1: 2-1: 6 to obtain an alcohol solution;
s13, sequentially adding calcium sulfate, silicon dioxide, an activating agent and a coupling agent into the alcoholic solution obtained in the step S12, uniformly mixing by using a high-speed mixer, transferring into a reaction kettle, and reacting for 0.8-3.2 hours at the temperature of 100-150 ℃; after the reaction is finished, placing the mixed material in a drying oven for drying, controlling the temperature of the drying oven to be 80-100 ℃, and drying for 3-5 hours to obtain modified activated hydrocarbon resin;
s2, preparing a solid acid catalyst precursor;
s21, mixing AlCl3Solution and Na2SiO3Uniformly mixing the solutions according to the volume ratio of 1: 2-1: 5, adding an isovolumetric barium hydroxide solution into the mixed solution, and standing for 1-2 hours to obtain a solution A; wherein the AlCl3The concentration of the solution is 0.2mol/L, and the Na2SiO3The concentration of the solution is 0.3mol/L, and the concentration of the barium hydroxide solution is 0.25 mol/L;
s22, adding 0.1-0.5 mol/L ammonium chloride solution into the solution A obtained in the step S21, and carrying out ion exchange reaction to obtain a solid acid catalyst precursor; wherein the ion exchange reaction temperature is controlled to be 50-70 ℃, and the volume ratio of the ammonium chloride solution to the solution A is 1: 5-1: 13;
s3, loading the modified hydrocarbon resin by using a solid acid catalyst;
crushing the modified and activated hydrocarbon resin obtained in the step S13, sieving the crushed modified and activated hydrocarbon resin with a 300-600-mesh sieve, and then carrying out vacuum drying in a drying oven at the temperature of 70-90 ℃ for 2-4 h; and (4) adding the solid acid catalyst precursor obtained in the step (S22) according to the solid-to-liquid ratio of 3: 1-7: 1, diluting with absolute ethyl alcohol of which the volume is 3-5 times that of the solid acid catalyst precursor, stirring for 1-5 h, carrying out suction filtration, washing, and vacuum drying to obtain the modified solid acid catalyst taking hydrocarbon resin as a carrier.
Further, in step S11, the activator is a mixture of activated magnesium oxide and stearic acid at a weight ratio of 7:1, and the use of the activator composed of magnesium oxide and stearic acid can promote the interfacial activity of the polyolefin resin and the polyphenylene sulfone resin.
Further, in step S11, the coupling agent is a mixture of equal volumes of a titanate coupling agent and an aluminate coupling agent, and the interfacial properties of the polyolefin resin and the polyphenylene sulfone resin can be changed by adding the mixture of the titanate coupling agent and the aluminate coupling agent.
Further, in step S13, when the high-speed mixer is used to mix the materials, the materials are mixed at a rotation speed of 600-1200 rpm for 15-25 min, then mixed at a rotation speed of 200-500 rpm for 5-8 min, the high rotation speed is used first, and then the low rotation speed is used to mix the materials, so that the activating agent can be uniformly dispersed on the surfaces of the polyolefin resin and the polyphenylene sulfone resin, and the organic group in the activating agent faces outwards to form steric hindrance, thereby forming a stable interface layer and effectively preventing the agglomeration of the polyolefin resin and the polyphenylene sulfone resin.
Further, after step S21 is completed, the solution A is placed in an ultrasonic auxiliary device, the frequency of the ultrasonic auxiliary device is controlled to be 20-40 KHz, the ultrasonic power is controlled to be 600-1000W, and AlCl can be enabled by using the ultrasonic auxiliary device3Solution, Na2SiO3The solution and barium hydroxide solution were mixed thoroughly.
Further, after the step S3 is completed, the obtained modified solid acid catalyst with hydrocarbon resin as a carrier is washed with deionized water until the solution is neutral, the neutral solution does not corrode equipment, and no wastewater is discharged, so that the modified solid acid catalyst with hydrocarbon resin as a carrier prepared by the method of the present invention is more environment-friendly and practical.
Further, in step S13, the high-speed mixer includes a mixing cylinder, a stirring assembly and a vibration assembly, the bottom of the mixing cylinder is provided with a base, and the upper end of the mixing cylinder is provided with a feed inlet and an exhaust outlet; the stirring assembly comprises a speed regulating motor, a stirrer and a speed regulating switch, the speed regulating motor is fixedly arranged at the top end of the outer part of the mixing barrel, an output shaft of the speed regulating motor vertically penetrates through the mixing barrel, the stirrer is vertically arranged inside the mixing barrel, the stirrer is fixedly connected with the output shaft of the speed regulating motor, the speed regulating switch is fixedly arranged on the side wall of the mixing tool, and the speed regulating switch is electrically connected with the speed regulating motor; the vibration assembly comprises a power motor, a piston plate, a vibration plate and a vibration cam, the power motor is fixedly arranged on the base, a first belt wheel is arranged on an output shaft of the power motor, the piston plate is hermetically clamped inside the mixing barrel and is positioned at the lower end of the stirrer, a sliding rod is arranged at the bottom of the piston plate, a sliding sleeve is arranged on the inner wall of the mixing barrel, the sliding rod is movably sleeved on the sliding sleeve, a reset spring is sleeved on the sliding rod, one end of the reset spring is abutted to the sliding sleeve, the other end of the reset spring is abutted to the bottom end of the sliding rod, the vibration plate is fixedly arranged at the lower end of the sliding rod, the vibration cam is fixedly arranged at the bottom end inside the mixing barrel through an installation seat; the speed regulating motor and the power motor are powered by an external power supply, the speed regulating motor is a YS8024 type three-phase asynchronous motor produced by Ningbo power motor company Limited, the power motor is a M2IK90N-C type single-phase asynchronous motor produced by Kunzhan doubly Ente electromechanical company Limited, the speed regulating switch is an LW5-16A-002-3 type motor speed regulating change-over switch produced by Taizhou Mingjia electrical source manufacturers, a piston plate capable of vibrating up and down is arranged inside the mixing barrel, the mixing efficiency and the effect of materials can be obviously improved, and meanwhile the materials can be prevented from being bonded on the inner wall of the mixing barrel.
The working principle of the high-speed mixer is as follows: during the use, for buncher and motor power supply through external power source, with during alcoholic solution, calcium sulfate, silica, activator, coupling agent loop through the leading-in compounding section of thick bamboo of feed inlet, through the rotational speed of speed governing switch control buncher, stir the mixture in the room through the agitator, it is rotatory to drive vibrations cam through motor power, vibrations cam rotation in-process drives the vibrations board and reciprocates, and then makes the slide bar of piston plate bottom reciprocate in the sliding sleeve, the mixed effect of promotion material.
Compared with the prior art, the invention has the beneficial effects that: the method has the advantages of mild reaction conditions, simple and easy operation and low cost; the solid acid catalyst prepared by the method and taking the hydrocarbon resin as the carrier has stronger acidity, is simple to separate from a liquid phase reaction system and simple to post-treat, reduces the corrosion of equipment, is environment-friendly and pollution-free in production, and can be recycled; polyolefin resin and polyphenylene sulfone resin are used as carrier materials, so that the prepared solid acid catalyst taking hydrocarbon resin as a carrier has larger specific surface area and higher porosity, the reaction time can be shortened, and the yield of the product can be improved; by adding an activator and a coupling agent to a mixture of a polyolefin resin and a polyphenylene sulfone resin, the interfacial activity of the polyolefin resin and the polyphenylene sulfone resin can be promoted, and the interfacial properties of the polyolefin resin and the polyphenylene sulfone resin can be improved.
Drawings
FIG. 1 is a schematic structural view of a high mixing machine of the present invention;
the device comprises a mixing barrel 1, a base 10, a feed inlet 11, an exhaust port 12, a sliding sleeve 13, a stirring assembly 2, a speed regulating motor 20, a stirrer 21, a speed regulating switch 22, a vibration assembly 3, a power motor 30, a pulley 300, a piston plate 31, a sliding rod 310, a reset spring 311, a vibration plate 32, a vibration cam 33, a mounting seat 330, a pulley 331 and a belt 332.
Detailed Description
Example 1: a preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier comprises the following steps:
s1, modifying and activating hydrocarbon resin;
s11, respectively weighing the following raw materials in parts by weight: 35 parts of polyolefin resin, 10 parts of polyphenylene sulfone resin, 5 parts of calcium sulfate, 3 parts of silicon dioxide, 0.8 part of activating agent and 0.5 part of coupling agent; the activator is formed by mixing active magnesium oxide and stearic acid according to the weight ratio of 7:1, and the surfactant consisting of the magnesium oxide and the stearic acid can promote the interfacial activity of polyolefin resin and polyphenylene sulfone resin; the coupling agent is a mixture composed of a titanate coupling agent and an aluminate coupling agent in equal volumes, and the interface performance of the polyolefin resin and the polyphenylene sulfone resin can be changed by adding the mixture of the titanate coupling agent and the aluminate coupling agent;
s12, fully stirring and mixing the polyolefin resin and the polyphenylene sulfone resin weighed in the step S11 to form a mixed material, and uniformly mixing the mixed material and absolute ethyl alcohol according to the volume ratio of 1:2 to obtain an alcohol solution;
s13, sequentially adding calcium sulfate, silicon dioxide, an activating agent and a coupling agent into the alcoholic solution obtained in the step S12, uniformly mixing by using a high-speed mixer, transferring into a reaction kettle, and reacting for 0.8h at the temperature of 100 ℃; after the reaction is finished, placing the mixed material in a drying oven for drying, controlling the temperature of the drying oven to be 80 ℃ and the drying time to be 3h to obtain modified activated hydrocarbon resin;
s2, preparing a solid acid catalyst precursor;
s21, mixing AlCl3Solution and Na2SiO3Uniformly mixing the solution according to the volume ratio of 1:2, adding an isometric barium hydroxide solution into the mixed solution, and standing for 1h to obtain a solution A; AlCl3The concentration of the solution is 0.2mol/L, Na2SiO3The concentration of the solution is 0.3mol/L, and the concentration of the barium hydroxide solution is 0.25 mol/L;
s22, adding 0.1mol/L ammonium chloride solution into the solution A obtained in the step S21, and carrying out ion exchange reaction to obtain a solid acid catalyst precursor; wherein the ion exchange reaction temperature is controlled to be 50 ℃, and the volume ratio of the ammonium chloride solution to the solution A is 1: 5;
s3, loading the modified hydrocarbon resin by using a solid acid catalyst;
crushing the modified activated hydrocarbon resin obtained in the step S13, sieving the crushed resin by a 300-mesh sieve, and then carrying out vacuum drying in a drying oven at the temperature of 70 ℃ for 2 hours; and (3) adding the solid acid catalyst precursor obtained in the step (S22) according to the solid-to-liquid ratio of 3:1, diluting with absolute ethyl alcohol of which the volume is 3 times that of the solid acid catalyst precursor, stirring for 1h, carrying out suction filtration, washing, and carrying out vacuum drying to obtain the modified solid acid catalyst taking hydrocarbon resin as a carrier.
Example 2: a preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier comprises the following steps:
s1, modifying and activating hydrocarbon resin;
s11, respectively weighing the following raw materials in parts by weight: 40 parts of polyolefin resin, 12 parts of polyphenylene sulfone resin, 5 parts of calcium sulfate, 4 parts of silicon dioxide, 1.12 parts of activating agent and 0.5 part of coupling agent; the activator is formed by mixing active magnesium oxide and stearic acid according to the weight ratio of 7:1, and the surfactant consisting of the magnesium oxide and the stearic acid can promote the interfacial activity of polyolefin resin and polyphenylene sulfone resin; the coupling agent is a mixture composed of a titanate coupling agent and an aluminate coupling agent in equal volumes, and the interface performance of the polyolefin resin and the polyphenylene sulfone resin can be changed by adding the mixture of the titanate coupling agent and the aluminate coupling agent;
s12, fully stirring and mixing the polyolefin resin and the polyphenylene sulfone resin weighed in the step S11 to form a mixed material, and uniformly mixing the mixed material and absolute ethyl alcohol according to the volume ratio of 1:4 to obtain an alcohol solution;
s13, sequentially adding calcium sulfate, silicon dioxide, an activating agent and a coupling agent into the alcoholic solution obtained in the step S12, uniformly mixing by using a high-speed mixer, transferring into a reaction kettle, and reacting for 2.4 hours at the temperature of 135 ℃; after the reaction is finished, placing the mixed material in a drying oven for drying, controlling the temperature of the drying oven to be 91 ℃ and the drying time to be 45h to obtain modified activated hydrocarbon resin; when a high-speed mixer is used for mixing materials, the materials are mixed for 18min at the rotating speed of 700rpm, then mixed for 6min at the rotating speed of 3000rpm, the materials are mixed at the high rotating speed and then at the low rotating speed, so that the activating agent can be uniformly dispersed on the surfaces of the polyolefin resin and the polyphenylene sulfone resin, organic groups in the activating agent face outwards to form steric hindrance, a stable interface layer is formed, and the agglomeration of the polyolefin resin and the polyphenylene sulfone resin is effectively prevented.
S2, preparing a solid acid catalyst precursor;
s21, mixing AlCl3Solution and Na2SiO3Uniformly mixing the solution according to the volume ratio of 1:3, adding an equal volume of barium hydroxide solution into the mixed solution, and standing for 1.3 hours to obtain a solution A; wherein, AlCl3The concentration of the solution is 0.2mol/L, Na2SiO3The concentration of the solution is 0.3mol/L, and the concentration of the barium hydroxide solution is 0.25 mol/L;
s22, adding 0.3mol/L ammonium chloride solution into the solution A obtained in the step S21, and carrying out ion exchange reaction to obtain a solid acid catalyst precursor; wherein the ion exchange reaction temperature is controlled to be 63 ℃, and the volume ratio of the ammonium chloride solution to the solution A is 1: 8;
s3, loading the modified hydrocarbon resin by using a solid acid catalyst;
crushing the modified and activated hydrocarbon resin obtained in the step S13, passing through a 560-mesh sieve, and then carrying out vacuum drying in a drying oven at the temperature of 85 ℃ for 3 hours; and (4) adding the solid acid catalyst precursor obtained in the step (S22) according to the solid-to-liquid ratio of 5:1, diluting with absolute ethyl alcohol of which the volume is 4 times that of the solid acid catalyst precursor, stirring for 3 hours, carrying out suction filtration, washing, and vacuum drying to obtain the modified solid acid catalyst taking hydrocarbon resin as a carrier.
Example 3: a preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier comprises the following steps:
s1, modifying and activating hydrocarbon resin;
s11, respectively weighing the following raw materials in parts by weight: 50 parts of polyolefin resin, 15 parts of polyphenylene sulfone resin, 8 parts of calcium sulfate, 5 parts of silicon dioxide, 1.2 parts of activating agent and 1 part of coupling agent; the activator is formed by mixing active magnesium oxide and stearic acid according to the weight ratio of 7:1, and the surfactant consisting of the magnesium oxide and the stearic acid can promote the interfacial activity of polyolefin resin and polyphenylene sulfone resin; the coupling agent is a mixture composed of a titanate coupling agent and an aluminate coupling agent in equal volumes, and the interface performance of the polyolefin resin and the polyphenylene sulfone resin can be changed by adding the mixture of the titanate coupling agent and the aluminate coupling agent;
s12, fully stirring and mixing the polyolefin resin and the polyphenylene sulfone resin weighed in the step S11 to form a mixed material, and uniformly mixing the mixed material and absolute ethyl alcohol according to the volume ratio of 1:6 to obtain an alcohol solution;
s13, sequentially adding calcium sulfate, silicon dioxide, an activating agent and a coupling agent into the alcoholic solution obtained in the step S12, uniformly mixing by using a high-speed mixer, transferring into a reaction kettle, and reacting for 3.2 hours at the temperature of 150 ℃; after the reaction is finished, placing the mixed material in a drying oven for drying, controlling the temperature of the drying oven to be 100 ℃ and the drying time to be 5h to obtain modified activated hydrocarbon resin; when a high-speed mixer is used for mixing materials, firstly, the materials are mixed for 25min at the rotating speed of 1200rpm, then, the materials are mixed for 8min at the rotating speed of 500rpm, firstly, the materials are mixed at high rotating speed, then, the materials are mixed at low rotating speed, so that the activating agent can be uniformly dispersed on the surfaces of the polyolefin resin and the polyphenylene sulfone resin, the organic group in the activating agent faces outwards to form steric hindrance, a stable interface layer is formed, and the agglomeration of the polyolefin resin and the polyphenylene sulfone resin is effectively prevented;
s2, preparing a solid acid catalyst precursor;
s21, mixing AlCl3Solution and Na2SiO3Solution pressUniformly mixing according to the volume ratio of 1:5, adding an isometric barium hydroxide solution into the mixed solution, and standing for 2 hours to obtain a solution A; AlCl3The concentration of the solution is 0.2mol/L, Na2SiO3The concentration of the solution is 0.3mol/L, and the concentration of the barium hydroxide solution is 0.25 mol/L; placing the solution A into ultrasonic auxiliary equipment, controlling the frequency of the ultrasonic auxiliary equipment to be 20-40 KHz, controlling the ultrasonic power to be 600-1000W, and enabling AlCl to be achieved by using the ultrasonic auxiliary equipment3Solution, Na2SiO3Fully mixing the solution and the barium hydroxide solution;
s22, adding 0.5mol/L ammonium chloride solution into the solution A obtained in the step S21, and carrying out ion exchange reaction to obtain a solid acid catalyst precursor; wherein the ion exchange reaction temperature is controlled to be 70 ℃, and the volume ratio of the ammonium chloride solution to the solution A is 1: 13;
s3, loading the modified hydrocarbon resin by using a solid acid catalyst;
crushing the modified activated hydrocarbon resin obtained in the step S13, sieving the crushed resin with a 600-mesh sieve, and then carrying out vacuum drying in a drying oven at the temperature of 90 ℃ for 4 hours; and (4) adding the solid acid catalyst precursor obtained in the step (S22) according to the solid-to-liquid ratio of 7:1, diluting with absolute ethyl alcohol of which the volume is 5 times that of the solid acid catalyst precursor, stirring for 5 hours, carrying out suction filtration, washing, and carrying out vacuum drying to obtain the modified solid acid catalyst taking hydrocarbon resin as a carrier.
Example 4: a preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier comprises the following steps:
s1, modifying and activating hydrocarbon resin;
s11, respectively weighing the following raw materials in parts by weight: 50 parts of polyolefin resin, 15 parts of polyphenylene sulfone resin, 8 parts of calcium sulfate, 5 parts of silicon dioxide, 1.2 parts of activating agent and 1 part of coupling agent; the activator is formed by mixing active magnesium oxide and stearic acid according to the weight ratio of 7:1, and the surfactant consisting of the magnesium oxide and the stearic acid can promote the interfacial activity of polyolefin resin and polyphenylene sulfone resin; the coupling agent is a mixture composed of a titanate coupling agent and an aluminate coupling agent in equal volumes, and the interface performance of the polyolefin resin and the polyphenylene sulfone resin can be changed by adding the mixture of the titanate coupling agent and the aluminate coupling agent;
s12, fully stirring and mixing the polyolefin resin and the polyphenylene sulfone resin weighed in the step S11 to form a mixed material, and uniformly mixing the mixed material and absolute ethyl alcohol according to the volume ratio of 1:6 to obtain an alcohol solution;
s13, sequentially adding calcium sulfate, silicon dioxide, an activating agent and a coupling agent into the alcoholic solution obtained in the step S12, uniformly mixing by using a high-speed mixer, transferring into a reaction kettle, and reacting for 3.2 hours at the temperature of 150 ℃; after the reaction is finished, placing the mixed material in a drying oven for drying, controlling the temperature of the drying oven to be 100 ℃ and the drying time to be 5h to obtain modified activated hydrocarbon resin; when a high-speed mixer is used for mixing materials, firstly, the materials are mixed for 25min at the rotating speed of 1200rpm, then, the materials are mixed for 8min at the rotating speed of 500rpm, firstly, the materials are mixed at high rotating speed, then, the materials are mixed at low rotating speed, so that the activating agent can be uniformly dispersed on the surfaces of the polyolefin resin and the polyphenylene sulfone resin, the organic group in the activating agent faces outwards to form steric hindrance, a stable interface layer is formed, and the agglomeration of the polyolefin resin and the polyphenylene sulfone resin is effectively prevented;
s2, preparing a solid acid catalyst precursor;
s21, mixing AlCl3Solution and Na2SiO3Uniformly mixing the solution according to the volume ratio of 1:5, adding an isometric barium hydroxide solution into the mixed solution, and standing for 2 hours to obtain a solution A; AlCl3The concentration of the solution is 0.2mol/L, Na2SiO3The concentration of the solution is 0.3mol/L, and the concentration of the barium hydroxide solution is 0.25 mol/L; placing the solution A into ultrasonic auxiliary equipment, controlling the frequency of the ultrasonic auxiliary equipment to be 20-40 KHz, controlling the ultrasonic power to be 600-1000W, and enabling AlCl to be achieved by using the ultrasonic auxiliary equipment3Solution, Na2SiO3Fully mixing the solution and the barium hydroxide solution;
s22, adding 0.5mol/L ammonium chloride solution into the solution A obtained in the step S21, and carrying out ion exchange reaction to obtain a solid acid catalyst precursor; wherein the ion exchange reaction temperature is controlled to be 70 ℃, and the volume ratio of the ammonium chloride solution to the solution A is 1: 13;
s3, loading the modified hydrocarbon resin by using a solid acid catalyst;
crushing the modified activated hydrocarbon resin obtained in the step S13, sieving the crushed resin with a 600-mesh sieve, and then carrying out vacuum drying in a drying oven at the temperature of 90 ℃ for 4 hours; adding the solid acid catalyst precursor obtained in the step S22 according to the solid-to-liquid ratio of 7:1, diluting with absolute ethyl alcohol of which the volume is 5 times that of the solid acid catalyst precursor, stirring for 5 hours, carrying out suction filtration, washing, and carrying out vacuum drying to obtain a modified solid acid catalyst taking hydrocarbon resin as a carrier; the obtained modified solid acid catalyst taking the hydrocarbon resin as the carrier is washed by deionized water until the solution is neutral, the neutral solution can not corrode equipment, and no wastewater is discharged, so that the modified solid acid catalyst taking the hydrocarbon resin as the carrier prepared by the invention is more environment-friendly and practical.
Example 5: a preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier comprises the following steps:
s1, modifying and activating hydrocarbon resin;
s11, respectively weighing the following raw materials in parts by weight: 50 parts of polyolefin resin, 15 parts of polyphenylene sulfone resin, 8 parts of calcium sulfate, 5 parts of silicon dioxide, 1.2 parts of activating agent and 1 part of coupling agent; the activator is formed by mixing active magnesium oxide and stearic acid according to the weight ratio of 7:1, and the surfactant consisting of the magnesium oxide and the stearic acid can promote the interfacial activity of polyolefin resin and polyphenylene sulfone resin; the coupling agent is a mixture composed of a titanate coupling agent and an aluminate coupling agent in equal volumes, and the interface performance of the polyolefin resin and the polyphenylene sulfone resin can be changed by adding the mixture of the titanate coupling agent and the aluminate coupling agent;
s12, fully stirring and mixing the polyolefin resin and the polyphenylene sulfone resin weighed in the step S11 to form a mixed material, and uniformly mixing the mixed material and absolute ethyl alcohol according to the volume ratio of 1:6 to obtain an alcohol solution;
s13, sequentially adding calcium sulfate, silicon dioxide, an activating agent and a coupling agent into the alcoholic solution obtained in the step S12, uniformly mixing by using a high-speed mixer, transferring into a reaction kettle, and reacting for 3.2 hours at the temperature of 150 ℃; after the reaction is finished, placing the mixed material in a drying oven for drying, controlling the temperature of the drying oven to be 100 ℃ and the drying time to be 5h to obtain modified activated hydrocarbon resin; when a high-speed mixer is used for mixing materials, firstly, the materials are mixed for 25min at the rotating speed of 1200rpm, then, the materials are mixed for 8min at the rotating speed of 500rpm, firstly, the materials are mixed at high rotating speed, then, the materials are mixed at low rotating speed, so that the activating agent can be uniformly dispersed on the surfaces of the polyolefin resin and the polyphenylene sulfone resin, the organic group in the activating agent faces outwards to form steric hindrance, a stable interface layer is formed, and the agglomeration of the polyolefin resin and the polyphenylene sulfone resin is effectively prevented; the high-speed mixer comprises a mixing cylinder 1, a stirring component 2 and a vibration component 3, wherein a base 10 is arranged at the bottom of the mixing cylinder 1, and a feeding hole 11 and an exhaust hole 12 are arranged at the upper end of the mixing cylinder 1; the stirring assembly 2 comprises a speed regulating motor 20, a stirrer 21 and a speed regulating switch 22, wherein the speed regulating motor 20 is fixedly arranged at the top end of the outer part of the mixing cylinder 1, an output shaft of the speed regulating motor 20 vertically penetrates through the mixing cylinder 1, the stirrer 21 is vertically arranged inside the mixing cylinder 1, the stirrer 21 is fixedly connected with the output shaft of the speed regulating motor 20, the speed regulating switch 22 is fixedly arranged on the side wall of the mixing cylinder 1, and the speed regulating switch 22 is electrically connected with the speed regulating motor 20; the vibration component 3 comprises a power motor 30, a piston plate 31, a vibration plate 32 and a vibration cam 33, the power motor 30 is fixedly arranged on the base 10, a first belt wheel 300 is arranged on an output shaft of the power motor 30, the piston plate 31 is hermetically clamped in the mixing barrel 1 and is positioned at the lower end of the stirrer 21, a sliding rod 310 is arranged at the bottom of the piston plate 31, a sliding sleeve 13 is arranged on the inner wall of the mixing barrel 1, the sliding rod 310 is movably sleeved on the sliding sleeve 13, a reset spring 311 is sleeved on the sliding rod 310, one end of the reset spring 311 is abutted against the sliding sleeve 13, the other end of the reset spring is abutted against the bottom end of the sliding rod 310, the vibration plate 32 is fixedly arranged at the lower end of the sliding rod 310, the vibration cam 33 is fixedly arranged at the bottom end in the mixing barrel 1 through an installation seat 330, a second belt wheel 331; the speed regulating motor 20 and the power motor 30 are both powered by an external power supply, the speed regulating motor 20 is a YS8024 type three-phase asynchronous motor produced by Ningbo power motor company Limited, the power motor 30 is an M2IK90N-C type single-phase asynchronous motor produced by Kunshan Bint electromechanical company Limited, the speed regulating switch 22 is an LW5-16A-002-3 type motor speed regulating change-over switch produced by Taizhou Mingjia electrical source manufacturers, and the piston plate 31 capable of vibrating up and down is arranged in the mixing cylinder 1, so that the mixing efficiency and effect of materials can be obviously improved, and the materials can be prevented from being bonded on the inner wall of the mixing cylinder 1;
s2, preparing a solid acid catalyst precursor;
s21, mixing AlCl3Solution and Na2SiO3Uniformly mixing the solution according to the volume ratio of 1:5, adding an isometric barium hydroxide solution into the mixed solution, and standing for 2 hours to obtain a solution A; AlCl3The concentration of the solution is 0.2mol/L, Na2SiO3The concentration of the solution is 0.3mol/L, and the concentration of the barium hydroxide solution is 0.25 mol/L; placing the solution A into ultrasonic auxiliary equipment, controlling the frequency of the ultrasonic auxiliary equipment to be 20-40 KHz, controlling the ultrasonic power to be 600-1000W, and enabling AlCl to be achieved by using the ultrasonic auxiliary equipment3Solution, Na2SiO3Fully mixing the solution and the barium hydroxide solution;
s22, adding 0.5mol/L ammonium chloride solution into the solution A obtained in the step S21, and carrying out ion exchange reaction to obtain a solid acid catalyst precursor; wherein the ion exchange reaction temperature is controlled to be 70 ℃, and the volume ratio of the ammonium chloride solution to the solution A is 1: 13;
s3, loading the modified hydrocarbon resin by using a solid acid catalyst;
crushing the modified activated hydrocarbon resin obtained in the step S13, sieving the crushed resin with a 600-mesh sieve, and then carrying out vacuum drying in a drying oven at the temperature of 90 ℃ for 4 hours; adding the solid acid catalyst precursor obtained in the step S22 according to the solid-to-liquid ratio of 7:1, diluting with absolute ethyl alcohol of which the volume is 4 times that of the solid acid catalyst precursor, stirring for 5 hours, carrying out suction filtration, washing, and vacuum drying to obtain a modified solid acid catalyst taking hydrocarbon resin as a carrier; the obtained modified solid acid catalyst taking the hydrocarbon resin as the carrier is washed by deionized water until the solution is neutral, the neutral solution can not corrode equipment, and no wastewater is discharged, so that the modified solid acid catalyst taking the hydrocarbon resin as the carrier prepared by the invention is more environment-friendly and practical.
The high-speed mixer comprises a mixing cylinder 1, a stirring component 2 and a vibration component 3, wherein a base 10 is arranged at the bottom of the mixing cylinder 1, and a feeding hole 11 and an exhaust hole 12 are arranged at the upper end of the mixing cylinder 1; the stirring assembly 2 comprises a speed regulating motor 20, a stirrer 21 and a speed regulating switch 22, wherein the speed regulating motor 20 is fixedly arranged at the top end of the outer part of the mixing cylinder 1, an output shaft of the speed regulating motor 20 vertically penetrates through the mixing cylinder 1, the stirrer 21 is vertically arranged inside the mixing cylinder 1, the stirrer 21 is fixedly connected with the output shaft of the speed regulating motor 20, the speed regulating switch 22 is fixedly arranged on the side wall of the mixing cylinder 1, and the speed regulating switch 22 is electrically connected with the speed regulating motor 20; the vibration component 3 comprises a power motor 30, a piston plate 31, a vibration plate 32 and a vibration cam 33, the power motor 30 is fixedly arranged on the base 10, a first belt wheel 300 is arranged on an output shaft of the power motor 30, the piston plate 31 is hermetically clamped in the mixing barrel 1 and is positioned at the lower end of the stirrer 21, a sliding rod 310 is arranged at the bottom of the piston plate 31, a sliding sleeve 13 is arranged on the inner wall of the mixing barrel 1, the sliding rod 310 is movably sleeved on the sliding sleeve 13, a reset spring 311 is sleeved on the sliding rod 310, one end of the reset spring 311 is abutted against the sliding sleeve 13, the other end of the reset spring is abutted against the bottom end of the sliding rod 310, the vibration plate 32 is fixedly arranged at the lower end of the sliding rod 310, the vibration cam 33 is fixedly arranged at the bottom end in the mixing barrel 1 through an installation seat 330, a second belt wheel 331; the speed regulating motor 20 and the power motor 30 are powered by an external power supply, the speed regulating motor 20 is a YS8024 type three-phase asynchronous motor produced by Ningbo power motor company Limited, the power motor 30 is a M2IK90N-C type single-phase asynchronous motor produced by Kunshan Bint electromechanical company Limited, the speed regulating switch 22 is an LW5-16A-002-3 type motor speed regulating change-over switch produced by Taizhou Mingjia electrical source manufacturers, and the piston plate 31 capable of vibrating up and down is arranged inside the mixing cylinder 1, so that the mixing efficiency and the mixing effect of materials can be obviously improved, and meanwhile, the materials can be prevented from being bonded on the inner wall of the mixing cylinder 1.
Test example: the modified solid acid catalysts obtained in examples 1 to 5 using hydrocarbon resins as carriers were examined, and the results are shown in Table 1;
table 1 chemical properties of modified solid acid catalysts supported on hydrocarbon resins under different reaction conditions;
| examples | 1 | 2 | 3 | 4 | 5 |
| |
32 | 24 | 25 | 32 | 34 |
| Conversion rate/% | 95.5 | 92.3 | 93.4 | 96.5 | 97.6 |
As can be seen from table 1, the solid acid catalyst prepared by the present invention using hydrocarbon resin as a carrier has high catalytic activity, good selectivity, easy separation and recovery, and high cycle stability.
Claims (8)
1. A preparation method of a modified solid acid catalyst taking hydrocarbon resin as a carrier is characterized by comprising the following steps:
s1, modifying and activating hydrocarbon resin;
s11, respectively weighing the following raw materials in parts by weight: 35-50 parts of polyolefin resin, 10-15 parts of polyphenylene sulfone resin, 5-8 parts of calcium sulfate, 3-5 parts of silicon dioxide, 0.8-1.2 parts of activating agent and 0.5-1 part of coupling agent;
s12, fully stirring and mixing the polyolefin resin and the polyphenylene sulfone resin weighed in the step S11 to form a mixed material, and uniformly mixing the mixed material and absolute ethyl alcohol according to the volume ratio of 1: 2-1: 6 to obtain an alcohol solution;
s13, sequentially adding calcium sulfate, silicon dioxide, an activating agent and a coupling agent into the alcoholic solution obtained in the step S12, uniformly mixing by using a high-speed mixer, transferring into a reaction kettle, and reacting for 0.8-3.2 hours at the temperature of 100-150 ℃; after the reaction is finished, placing the mixed material in a drying oven for drying, controlling the temperature of the drying oven to be 80-100 ℃, and drying for 3-5 hours to obtain modified activated hydrocarbon resin;
s2, preparing a solid acid catalyst precursor;
s21, mixing AlCl3Solution and Na2SiO3Uniformly mixing the solutions according to the volume ratio of 1: 2-1: 5, adding an isovolumetric barium hydroxide solution into the mixed solution, and standing for 1-2 hours to obtain a solution A; wherein the AlCl3The concentration of the solution is 0.2mol/L, and the Na2SiO3The concentration of the solution is 0.3mol/L, and the concentration of the barium hydroxide solution is 0.25 mol/L;
s22, adding 0.1-0.5 mol/L ammonium chloride solution into the solution A obtained in the step S21, and carrying out ion exchange reaction to obtain a solid acid catalyst precursor; wherein the ion exchange reaction temperature is controlled to be 50-70 ℃, and the volume ratio of the ammonium chloride solution to the solution A is 1: 5-1: 13;
s3, loading the modified hydrocarbon resin by using a solid acid catalyst;
crushing the modified and activated hydrocarbon resin obtained in the step S13, sieving the crushed modified and activated hydrocarbon resin with a 300-600-mesh sieve, and then carrying out vacuum drying in a drying oven at the temperature of 70-90 ℃ for 2-4 h; and (4) adding the solid acid catalyst precursor obtained in the step (S22) according to the solid-to-liquid ratio of 3: 1-7: 1, diluting with absolute ethyl alcohol of which the volume is 3-5 times that of the solid acid catalyst precursor, stirring for 1-5 h, carrying out suction filtration, washing, and vacuum drying to obtain the modified solid acid catalyst taking hydrocarbon resin as a carrier.
2. The method of claim 1, wherein in step S11, the activator is a mixture of activated magnesium oxide and stearic acid at a weight ratio of 7: 1.
3. The method of claim 1, wherein in step S11, the coupling agent is a mixture of titanate coupling agent and aluminate coupling agent in equal volume.
4. The method of claim 1, wherein in step S13, when the high-speed mixer is used to mix the materials, the materials are mixed at 600-1200 rpm for 15-25 min and then at 200-500 rpm for 5-8 min.
5. The method for preparing the modified solid acid catalyst with hydrocarbon resin as the carrier according to claim 1, wherein after step S21 is completed, the solution a is placed in an ultrasonic auxiliary device, the frequency of the ultrasonic auxiliary device is controlled to be 20 to 40KHz, and the ultrasonic power is controlled to be 600 to 1000W.
6. The method according to claim 1, wherein after step S3, the obtained modified solid acid catalyst with hydrocarbon resin as a carrier is washed with deionized water until the solution becomes neutral.
7. The method for preparing a modified solid acid catalyst with hydrocarbon resin as carrier in claim 1, wherein in step S13, the high-speed mixer comprises a mixing drum (1), a stirring component (2) and a vibrating component (3), the mixing drum (1) is provided with a base (10) at the bottom, and the mixing drum (1) is provided with a feeding port (11) and an exhaust port (12) at the upper end; the stirring assembly (2) comprises a speed regulating motor (20), a stirrer (21) and a speed regulating switch (22), the speed regulating motor (20) is fixedly arranged at the top end of the outer part of the mixing barrel (1), an output shaft of the speed regulating motor (20) vertically penetrates through the mixing barrel (1), the stirrer (21) is vertically arranged inside the mixing barrel (1), the stirrer (21) is fixedly connected with the output shaft of the speed regulating motor (20), the speed regulating switch (22) is fixedly arranged on the side wall of the mixing barrel (1), and the speed regulating switch (22) is electrically connected with the speed regulating motor (20); the vibration component (3) comprises a power motor (30), a piston plate (31), a vibration plate (32) and a vibration cam (33), the power motor (30) is fixedly arranged on a base (10), a first belt wheel (300) is arranged on an output shaft of the power motor (30), the piston plate (31) is clamped inside the mixing barrel (1) in a sealing manner and is positioned at the lower end of the stirrer (21), a sliding rod (310) is arranged at the bottom of the piston plate (31), a sliding sleeve (13) is arranged on the inner wall of the mixing barrel (1), the sliding rod (310) is movably sleeved on the sliding sleeve (13), a reset spring (311) is sleeved on the sliding rod (310), one end of the reset spring (311) is abutted against the sliding sleeve (13), the other end of the reset spring is abutted against the bottom end of the sliding rod (310), the vibration plate (32) is fixedly arranged at the lower end of the sliding rod (310), the vibration cam (33) is fixedly arranged at the bottom end inside the mixing barrel (1) through, the vibration cam (33) is provided with a second belt wheel (331), and the second belt wheel (331) and the first belt wheel (300) are transmitted through a belt (332).
8. The method according to claim 1, wherein the modified solid acid catalyst supported on a hydrocarbon resin is washed with an ethanol solution until the solution becomes neutral after completion of step S3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010181447.9A CN111298837A (en) | 2020-03-16 | 2020-03-16 | Preparation method of modified solid acid catalyst with hydrocarbon resin as carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010181447.9A CN111298837A (en) | 2020-03-16 | 2020-03-16 | Preparation method of modified solid acid catalyst with hydrocarbon resin as carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111298837A true CN111298837A (en) | 2020-06-19 |
Family
ID=71153306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010181447.9A Pending CN111298837A (en) | 2020-03-16 | 2020-03-16 | Preparation method of modified solid acid catalyst with hydrocarbon resin as carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111298837A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112742247A (en) * | 2020-12-31 | 2021-05-04 | 江西建邦建设集团有限公司 | Straw natural pond liquid homogeneous mixing device for environmental protection marsh gas engineering |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
| CN106140297A (en) * | 2014-11-18 | 2016-11-23 | 北京林业大学 | A kind of resin esterification catalyst and preparation method thereof |
| CN106513024A (en) * | 2016-10-20 | 2017-03-22 | 陕西延长石油（集团）有限责任公司炼化公司 | Solid acid catalyst, and preparation method and application thereof |
| CN106519424A (en) * | 2016-09-29 | 2017-03-22 | 珠海格力电器股份有限公司 | Modified polypropylene resin and preparation method thereof |
| CN208612331U (en) * | 2018-06-20 | 2019-03-19 | 南京惠宇农化有限公司 | A kind of high frequency solid vibration chemical industry high mixer |
| CN109759043A (en) * | 2019-02-13 | 2019-05-17 | 郑州大学 | A kind of preparation method of solid acid catalyst and preparation method thereof and D-pHPG |
-
2020
- 2020-03-16 CN CN202010181447.9A patent/CN111298837A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
| CN106140297A (en) * | 2014-11-18 | 2016-11-23 | 北京林业大学 | A kind of resin esterification catalyst and preparation method thereof |
| CN106519424A (en) * | 2016-09-29 | 2017-03-22 | 珠海格力电器股份有限公司 | Modified polypropylene resin and preparation method thereof |
| CN106513024A (en) * | 2016-10-20 | 2017-03-22 | 陕西延长石油（集团）有限责任公司炼化公司 | Solid acid catalyst, and preparation method and application thereof |
| CN208612331U (en) * | 2018-06-20 | 2019-03-19 | 南京惠宇农化有限公司 | A kind of high frequency solid vibration chemical industry high mixer |
| CN109759043A (en) * | 2019-02-13 | 2019-05-17 | 郑州大学 | A kind of preparation method of solid acid catalyst and preparation method thereof and D-pHPG |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112742247A (en) * | 2020-12-31 | 2021-05-04 | 江西建邦建设集团有限公司 | Straw natural pond liquid homogeneous mixing device for environmental protection marsh gas engineering |
| CN112742247B (en) * | 2020-12-31 | 2022-12-06 | 江西建邦建设集团有限公司 | Straw natural pond liquid homogeneous mixing device for environmental protection marsh gas engineering |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105833918B (en) | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/ UiO-66-(COOH)2Preparation method and applications | |
| CN101791575B (en) | Preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals | |
| CN112808283A (en) | SrTiO3Microwave rapid preparation method of-BiOBr composite catalyst | |
| CN110420659B (en) | Device and method for catalytic oxidation of magnesium sulfite, cobalt nitrate/ZSM-5 molecular sieve catalyst and preparation method thereof | |
| CN111298837A (en) | Preparation method of modified solid acid catalyst with hydrocarbon resin as carrier | |
| CN2794624Y (en) | High efficiency reactor for high viscosity material solid liquid heterogeneous reaction | |
| CN102614919B (en) | Sulfonated cross-linked chitosan resin type solid acid catalyst and preparation method thereof | |
| CN103537284B (en) | Preparation method of nano-copper oxide catalyst for degrading organic dye wastewater | |
| CN1488438A (en) | Method for preparing titanium-silicon molecular sieve | |
| CN103127957B (en) | Mesoporous PW/MoO3-TiO2-SiO2 catalyst and preparation method and application thereof | |
| CN109675538A (en) | A kind of mixed crystal titanium dioxide R3-A2TiO2And its application in 5 hydroxymethyl furfural is prepared in catalysis glucose | |
| CN102627292B (en) | Preparation method of TS-1 molecular sieve | |
| CN113023746B (en) | Lanthanum modified molecular sieve and preparation method and application thereof | |
| CN205948772U (en) | Iron -phosphate mixing machine | |
| CN108295896B (en) | Method for catalytically producing alkylated gasoline | |
| CN100450925C (en) | Process for synthesizing mesoporous TiO2 using phosphotungstic acid as template agent | |
| CN204275970U (en) | A kind of reactor | |
| CN221062436U (en) | Stirrer for allyl glycidyl ether production | |
| CN103121979A (en) | Method for realizing epoxidation of olefins and air through catalysis of cobalt-contained catalyst under assistance of ultrasonic waves | |
| CN218307968U (en) | Reation kettle is used in cleaner production | |
| CN206746044U (en) | A kind of ionic-liquid catalyst regenerates extraction equipment | |
| CN110180587A (en) | The preparation method and applications of functionalized silicon nanometer sheet loaded palladium catalyst | |
| CN1810746A (en) | Cyclohexane selectively oxidizing process to prepare cyclohexanone and cyclohexanol | |
| CN220194663U (en) | Preparation facilities that low mercury catalyst was used | |
| CN104741147A (en) | Sulfonated cross-linked chitosan-SiO2 composite solid acid catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200619 |
|
| RJ01 | Rejection of invention patent application after publication |