CN112898248A - Preparation method of alkenyl succinic anhydride - Google Patents
Preparation method of alkenyl succinic anhydride Download PDFInfo
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- CN112898248A CN112898248A CN201911131728.7A CN201911131728A CN112898248A CN 112898248 A CN112898248 A CN 112898248A CN 201911131728 A CN201911131728 A CN 201911131728A CN 112898248 A CN112898248 A CN 112898248A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention discloses a preparation method of alkenyl succinic anhydride. The method comprises the following steps: after the mixture of the mixed internal olefin and the maleic anhydride is added with a heteropoly acid catalyst, heating and reacting to generate alkenyl succinic anhydride; the mixed internal olefin is a mixture of internal hexadecene and internal octadecene. The preparation method uses heteropoly acid as a catalyst. The heteropoly acid catalyst can perform the catalytic reaction of ASA, has high catalytic activity, and can perform high-efficiency catalytic reaction by adding a small amount of heteropoly acid catalyst into the solution; the corrosion of the vessel can be effectively avoided by using the acid-resistant reaction kettle, the separation is simple, no toxic or harmful gas is generated, and the environment is protected; the high-temperature-resistant paint has good temperature resistance, and the highest temperature resistance can reach 350 ℃; has good regeneration and reutilization performance, and the reutilization time in the reaction of catalyzing the generation of the ASA is more than 30 times. The purity of the alkenyl succinic anhydride product obtained by the invention is not lower than 99%, the reaction yield is more than 85%, and the method has high production practicability.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering and organic synthesis. More particularly, it relates to a method for preparing alkenyl succinic anhydride.
Background
Alkenyl Succinic anhydride is called as Alkenyl Succinic Anhydrides in English, called ASA for short, and is an important organic chemical raw material, and the structural formula of the Alkenyl Succinic anhydride is as follows:
wherein R is1And R2Is a linear alkyl radical, and R1And R2The sum of the carbon atoms in the carbon atoms is 13-15.
Alkenyl succinic anhydride has wide application, can be used as a rust remover for processing metal materials, a water repellent for silk fabrics, a hardening agent for various resins, a preservative for fiber products and lubricating oil for bearing joints, wherein the most important application is as a neutral sizing agent in papermaking. Compared with the traditional rosin sizing agent, the ASA sizing agent has the advantages of larger range of sizing pH, faster and better emulsification effect, good compatibility with various fillers or dyes, strong acid-base solution corrosion resistance, high paper strength and the like.
It has been reported in The literature that ASA was first prepared using stearic acid or a stearic acid homologue (H.M.teeter, M.J.Geerts, J.C.Cowan, Polymerization of Drying oils. III. Some oil emulsion Reaction of Maleic Anhydride with Methyl acid and Methyl alcohol II oil Chem so 25(1948)158-
With the maturity of petroleum cracking technology and olefin oligomerization technology, long-chain olefin required by raw materials can be provided in large quantity, and then the ASA can be generated by combining with maleic anhydride. The activation energy required for this reaction is high, so that the reaction needs to be carried out at a high temperature for a long time. A series of side reactions such as olefin self-polymerization and crosslinking, maleic anhydride self-polymerization and decomposition, olefin and maleic anhydride copolymerization and the like can occur in the reaction process at high temperature, so that the conversion rate of ASA is low, and the difficulty in subsequent separation and purification of ASA is increased. Although the literature reports that the above problems can be partially solved by adding a catalyst (U.S. Pat. No.3,412,111), a polymerization inhibitor (U.S. Pat. No.3,102,064) and an aromatic solvent (U.S. Pat. No.5,739,355), the disadvantages of complicated catalyst preparation process, relatively short catalyst service life, low recycling efficiency and the like still exist, and the requirements of industrialization of ASA production are difficult to meet.
The present invention therefore proposes a novel catalytic process for the preparation of alkenylsuccinic anhydrides and the catalysts used, solving at least one of the problems mentioned above.
Disclosure of Invention
The invention aims to provide a preparation method of alkenyl succinic anhydride, which uses heteropoly acid as a catalyst. The heteropoly acid catalyst can perform the catalytic reaction of ASA, has high catalytic activity, and can perform high-efficiency catalytic reaction by adding a small amount of heteropoly acid catalyst into the solution; the corrosion of the vessel can be effectively avoided by using the acid-resistant reaction kettle, the separation is simple, no toxic or harmful gas is generated, and the environment is protected; the high-temperature-resistant paint has good temperature resistance, and the highest temperature resistance can reach 350 ℃; has good regeneration and reutilization performance, and the reutilization time in the reaction of catalyzing the generation of the ASA is more than 30 times.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing alkenyl succinic anhydride, comprising the steps of:
after the mixture of the mixed internal olefin and the maleic anhydride is added with a heteropoly acid catalyst, heating and reacting to generate alkenyl succinic anhydride; the mixed internal olefin is a mixture of internal hexadecene and internal octadecene.
Wherein the internal hexadecene and the internal octadecene used are both linear internal olefins and contain a C ═ C bond structure in the internal position.
Heteropolyacids are acids formed from specific combinations of hydrogen and oxygen with certain metals and non-metals. Metal supplementation in heteropolyacidsAtoms are linked by oxygen atoms to form MO groups aggregated together around a central non-metallic heteroatom6Octahedron. The metal supplementing atoms include one or more of Mo, W, V, Ru, Rh, Sc, Cr, Mn, Co, Cu, Ni, Zn, Ce, Zr, Nb, Sb and Ti. The non-metallic heteroatoms include one or more of P, Si, As, Ge and B. Due to the MO6The octahedral and central non-metallic heteroatoms can be grouped together in a variety of possibilities, and heteropolyacids having a variety of structures can be prepared. Two of the more common heteropolyacids are the Keggin structure and the Dawson structure.
The Keggin heteropolyanions have the empirical formula XM12O40 n-Wherein X is a non-metallic heteroatom (e.g. P)5+、Si4+Or B3 +) And M is a metal-supplementing atom (e.g., Mo, W, V, Ce, Zr, Nb, Sb, and Ti). Exemplary Keggin heteropolyacids in which X is phosphorus include H3PW12O40、H3PMo12O40、H4PNbW11O40、H4PNbMo11O40、H4PVW11O40、H4PVMo11O40、H5PNb2W10O40、H5PNb2Mo10O40、H5PV2W10O40、H5PV2Mo10O40、H5PV2WMo9O40、H4PVW2Mo9O40、H6PV3W9O40、H6PV3Mo9O40、H5PCeW11O40、H3PW6Mo6O40、H7PV4W8O40、H7PV4Mo8O40、H5PZrW11O40And H5PTiW11O40. The phosphorus may be substituted with one or more other non-metallic heteroatoms as described above.
The Dawson heteropolyanion has the empirical formula X2M18O62 n-Wherein X is a non-metallic heteroatom and M is a metal supplementing atom. Exemplary Dawson heteropolyacids in which X is P include H6P2Mo18O62、H6P2W13Mo5O62、H6P2W14Mo4O62、H6P2W18O62And H6P2W17MoO62. The phosphorus may be substituted with one or more other non-metallic heteroatoms as described above. The Keggin anions and Dawson anions referred to herein may also include vacancy anions (i.e. those anions from which the structural fragment is absent). An exemplary Keggin-deficient anion is XM11O39 n-And XM9O34 n-。
In one embodiment, the heteropoly acid has a Keggin structure.
In another embodiment, the heteropoly acid is one or a combination of two or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsotungstic acid, arsenomolybdic acid, borotungstic acid, boromolybdic acid, germanotungstic acid, germanomolybdic acid, phosphotungstomolybdic acid, silicotungstomolybdic acid, arsotungstomolybdic acid, borotungstomolybdic acid, and germanotungstomolybdic acid.
In a particularly suitable embodiment, the heteropolyacid is one or a combination of two or more of phosphotungstic acid, phosphomolybdic acid and phosphotungstomolybdic acid.
Suitably, the heteropolyacid is phosphotungstic acid. More suitably, the phosphotungstic acid has a Keggin structure.
It will be appreciated that the heteropolyacid may be part of the catalytic complex.
In another embodiment, the heteropolyacid is obtained by a process as defined herein for the preparation of a heteropolyacid.
The heteropolyacid may be provided on a support. Any suitable support material may be used. Exemplary supports include alumina (e.g., alpha-Al)2O3Or gamma-Al2O3) Silica, alumina-silica, titaniaZeolites, kaolinites, clays, activated carbon, silicon carbide and mixtures thereof. Suitably, the heteropolyacid is provided on a silica support.
When the heteropolyacid is supported on a suitable support, the support constitutes from 0.1% to 90% of the total weight of the supported heteropolyacid. Suitably, the support constitutes from 0.1% to 30% of the total weight of the supported heteropolyacid. More suitably, the support constitutes from 15% to 25% of the total weight of the supported heteropolyacid.
In addition, the crystal water contained in the heteropoly-acid also influences the catalytic efficiency.
Preferably, the heteropolyacid contains one or more of crystal water numbers of 0, 6, 10, 14, 22 and 36.
Preferably, the heteropoly acid catalyst is solid powder, the microscopic surface is rough, and the specific surface area is very large.
Preferably, the heteropolyacid is phosphotungstic acid and has a value of ≥ 3m2BET surface area in g. More suitably, the heteropolyacid is phosphotungstic acid and has a value of ≥ 5m2BET surface area in g. Still more suitably, the heteropolyacid is phosphotungstic acid and has a molecular weight of 5m2/g-10m2BET surface area in g. The BET surface area may be represented by N2Physical adsorption analysis.
In one embodiment, the heteropolyacid is phosphotungstic acid and has a pore volume of from 0.1ml/g to 1.0 ml/g. More suitably, the heteropolyacid is phosphotungstic acid and has a pore volume of from 0.2ml/g to 0.8 ml/g. Still more suitably, the heteropolyacid is phosphotungstic acid and has a pore volume of from 0.2ml/g to 0.6 ml/g. Pore volume may be calculated using any suitable technique known in the art, such as, for example, the technique described in Fuel Processing Technology 135,2015, 195-202.
In one embodiment, the heteropolyacid is phosphotungstic acid and has a density of from 0.1g/ml to 20 g/ml. More suitably, the heteropolyacid is phosphotungstic acid and has a density of from 0.5g/ml to 15 g/ml. Still more suitably, the heteropolyacid is phosphotungstic acid and has a density of from 1g/ml to 10 g/ml. The Density may be calculated using any suitable technique known in the art, such as, for example, the technique described in the Stage 6Harmonization Text notification publication (Stage 6Harmonization Text notification) for "Bulk Density and Tapped Density" found on the United states Pharmacopeia website (http:// www.usp.org/usp-nf/harmony/Stage-6).
Preferably, the mole ratio of the internal hexadecene to the internal octadecene is 1: 1-4, and more preferably, the mole ratio of the internal hexadecene to the internal octadecene is 1: 1.
Preferably, the molar ratio of the maleic anhydride to the mixed internal olefin is 1: 1-4, and more preferably, the molar ratio of the maleic anhydride to the mixed internal olefin is 1: 2.
Preferably, the molar ratio of the heteropoly acid catalyst to the total reactant of the mixed internal olefin and the maleic anhydride is 1: 10-100, and more preferably, the molar ratio of the heteropoly acid catalyst to the total reactant of the mixed internal olefin and the maleic anhydride is 1: 50.
Preferably, the heating temperature is 150-250 ℃; further, in some embodiments of the present invention, for example, the heating temperature is 150 ℃ to 180 ℃, 180 ℃ to 200 ℃, 200 ℃ to 220 ℃, 220 ℃ to 250 ℃, or the like; most preferably, the heating temperature is from 200 ℃ to 220 ℃.
Preferably, after the temperature of the reaction system reaches 180 ℃, the heating rate is 9-13 ℃ per hour; more preferably, the rate of temperature rise is 10 ℃ per hour after the reaction system temperature reaches 180 ℃.
Preferably, the pressure of the reaction system is 100kPa to 1000 kPa; further, in some embodiments of the present invention, for example, the pressure of the reaction system is 100kPa to 200kPa, 200kPa to 400kPa, 400kPa to 600kPa, 600kPa to 800kPa, 800kPa to 1000kPa, or the like; most preferably, the pressure of the reaction system is 100kPa to 200 kPa.
Preferably, the reaction time is 5-20 h; further, in certain embodiments of the present invention, for example, the reaction time is 5 to 8 hours, 8 to 10 hours, 10 to 12 hours, 12 to 14 hours, 14 to 16 hours, 16 to 18 hours, 18 to 20 hours, etc.; most preferably, the time of the catalytic reaction is 16h to 18 h.
Preferably, stirring is carried out in the reaction process, and the stirring speed is 50-500 r/min; further, in some embodiments of the present invention, for example, the rotation speed of the stirring is 50 to 150 rpm, 150 to 300 rpm, 300 to 400 rpm, 400 to 500 rpm, etc.; most preferably, the rotation speed of the stirring is 150-300 r/min.
Preferably, the alkenylsuccinic anhydride preparation reaction is carried out in the absence of oxygen.
The heteropolyacid catalyst used in the present invention is prepared by the following method:
s1, mixing sodium tungstate, silicon dioxide, concentrated hydrochloric acid, concentrated phosphoric acid and distilled water, stirring uniformly, gradually heating to 50-90 ℃, stopping heating when the solid in the solution is completely dissolved and the color of the solution is changed into light yellow, and naturally cooling the system to room temperature to obtain a solution A;
s2, adding a solvent to extract the solution A to obtain a solution B;
and S3, removing the solvent in the solution B, and drying and calcining to obtain a solid C, namely the heteropoly acid catalyst.
Preferably, the preparation method of the heteropoly acid catalyst further comprises:
s4, grinding the solid C into powder, and collecting the solid powder heteropoly acid catalyst.
Preferably, the concentration of the concentrated hydrochloric acid is 10.0 wt.% to 38.0 wt.%, and the concentration of the concentrated phosphoric acid is 50.0 wt.% to 90.0 wt.%.
The preparation method has stable process, and the prepared solid super acidic heteropoly acid catalyst has the advantages of easy storage, difficult aging, long service life, recycling and the like, and solves the defects in the prior art.
Preferably, the molar ratio of the sodium tungstate to the silicon dioxide to the concentrated phosphoric acid is 15:1:1-1:1: 1.
Preferably, the volume ratio of the concentrated hydrochloric acid to the distilled water is 1:5 to 1: 10.
Preferably, the solvent is carbon tetrachloride, diethyl ether, 1, 2-dichloroethane, or ethanol. The solution a is extracted with a solvent to dissolve and extract to remove sodium tungstate and the like which have not reacted completely.
Preferably, solution a is extracted three more times in S2 to ensure complete extraction.
Preferably, the solution B in S3 is evaporated to remove the solvent. As understood by those skilled in the art, conventional methods for removing the solvent are possible, such as evaporation in the air at room temperature, or freeze-drying.
Preferably, the drying and calcining step described in S3 comprises: drying at 50-200 deg.c for 1-5 hr to constant weight, and calcining at 200-250 deg.c for 1-3 hr to control the crystal water content to proper amount.
In addition, unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
The invention has the following beneficial effects:
(1) the invention provides a heteropoly acid catalyst which is a solid super acidic catalyst and has high catalytic activity, and the catalyst has very high catalytic efficiency when the minimum addition amount reaches one percent in the reaction of catalyzing the generation of ASA; the catalyst is convenient to produce and store, green and environment-friendly, can be safely reacted by using an acid-resistant material, is simple to separate, and does not generate toxic and harmful substances or generate a large amount of gas in the catalytic reaction process; the high temperature resistance is good, and the highest temperature resistance can reach 350 ℃; has good regeneration and recycling performance, for example, the recycling frequency in the reaction of catalyzing the ASA generation is more than 30 times.
(2) The heteropoly acid catalyst is used for the generation reaction of alkenyl succinic anhydride, can generate ASA at a high speed and a high conversion rate, partially reduces the temperature required by the reaction, and can generate a large amount of ASA at the temperature of more than 200 ℃; the total reaction time is 14-18 h, and the process is safe and stable; the reaction is heterogeneous reaction, the catalyst is easy to separate and collect and can be repeatedly used, and the activity is not influenced; the purity of the obtained alkenyl succinic anhydride product is not lower than 99%, the reaction yield is more than 85%, and the method has high production practicability.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a scanning electron microscope image of a heteropoly acid catalyst prepared in example 1 of the present invention.
FIG. 2 shows the IR spectra of the heteropolyacid catalyst and the standard heteropolyacid catalyst obtained in example 1 of the present invention.
FIG. 3 shows the UV-visible absorption spectrum of the heteropoly-acid prepared in example 1 of the present invention.
Figure 4 compares the XRD patterns of the heteropolyacid catalyst prepared in example 1 with commercially available tungstophosphoric acid.
FIG. 5 shows infrared spectra of alkenylsuccinic anhydride and standard alkenylsuccinic anhydride obtained in example 1 of the present invention.
The specific implementation mode is as follows:
in order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The existing papermaking sizing process has low efficiency, expensive raw materials, unstable quality of papermaking products, difficult recovery and treatment of byproducts and great environmental hazard. In view of the above disadvantages, the present invention proposes a novel preparation method for synthesizing ASA for use in the sizing process of paper making. The method comprises the following steps: the target product ASA is synthesized efficiently and selectively by using endohexadecene, endooctadecene and maleic anhydride as raw materials and heteropoly acid as a catalyst, and the specific reaction formula is as follows:
in the formula R1And R2Is a straight chain alkyl radical, and R1、R2The sum of the numbers of the carbon atoms of the two is 13-15.
The method comprises the following specific operation steps: uniformly mixing internal hexadecene, internal octadecene and maleic anhydride, wherein the internal hexadecene and the internal octadecene are mixed according to the mass ratio of 1: 1-4, and the maleic anhydride and the internal olefin are mixed according to the molar ratio of 1: 1-4; adding a heteropoly acid catalyst, wherein the proportion of heteropoly acid to total reactants is 1: 10-100; continuously stirring and heating, and rapidly heating to 180 ℃; then carrying out catalytic reaction at 180-250 ℃ for 10-20 hours; after the reaction is finished, filtering out the catalyst, and distilling the solution under reduced pressure to remove excessive internal olefin (the internal olefin can be recycled for reuse) to obtain the product ASA.
The heteropoly acid catalyst can be phosphotungstic acid, preferably phosphotungstic acid containing 6 crystal water; or one or more of phosphomolybdic acid, phosphoarsenic acid and silicotungstic acid.
The purity of the endohexadecene and the endooctadecene is not less than 95%, and the mass ratio of the endohexadecene to the endooctadecene is preferably 1: 1.
The molar ratio of maleic anhydride to internal olefin is preferably 1: 2.
The ratio of the amount of the heteropoly acid catalyst to the total reaction mass is preferably 1: 50.
The stirring speed is preferably 150 to 300 revolutions per minute.
The reaction temperature is 180 ℃ to 250 ℃, and the preferable reaction temperature is 200 ℃ to 220 ℃.
The present invention will be further described with reference to the following specific examples.
Example 1
The preparation of heteropoly acid catalyst includes the following steps:
the method comprises the following steps: 50g of Na2WO4·2H2O and 5g SiO2The mixture was placed in a flask, and 5.6g of concentrated phosphoric acid having a concentration of 80 wt.% was added to the flask in 150mL of distilled water as a solvent, and the mixture was stirred without stopping and heated in a water bath. When the temperature is raised to 80 ℃, gradually dripping 46mL of concentrated hydrochloric acid with the percentage concentration of 35.5 percent, continuously raising the temperature to 90 ℃ until the solution is light yellow, stopping heating, and naturally cooling the solution to the room temperature.
Step two: transferring the solution prepared in the first step into a separating funnel under the conditions of 25 ℃ and 100kPa, adding 200mL of diethyl ether for extraction, separating the solution into three layers, and taking a bottom solution. The extraction was repeated three times and the bottom solution was collected.
Step three: naturally volatilizing the solvent from the base solution obtained in the second step in a fume hood, drying for 2h at 120 ℃ in a drying oven, and calcining for 2h at 240 ℃. And crushing and grinding the obtained solid sample to powder, and collecting to obtain the heteropoly acid catalyst.
FIG. 1 is a scanning electron microscope image of the obtained heteropoly acid catalyst, and it can be seen that the particle shape is neat and the size distribution is uniform.
FIG. 2 is an infrared spectrum of the resulting heteropolyacid catalyst and a standard heteropolyacid catalyst; the two infrared spectra are matched: 1080cm-1is-P-OaPeak of stretching vibration, 980cm-1is-W ═ ObPeak of extension and contraction vibration, 890cm-1Nearby is-W-ObW peak of stretching vibration, 800cm-1Nearby is-W-Oc-W peak of stretching vibration, 600cm-1The vicinity is an-O-H out-of-plane bending vibration absorption peak.
FIG. 3 shows a UV-visible absorption spectrum of the heteropoly-acid prepared in example 1, and the maximum absorption peak of UV-visible light of the heteropoly-acid is 314 nm.
Figure 4 compares the XRD patterns of the heteropolyacid catalyst prepared in example 1 with commercially available tungstophosphoric acid. The XRD patterns are basically consistent, which shows that the catalyst prepared according to example 1 is phosphotungstic acid.
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 88%.
FIG. 5 is an infrared spectrum of the resulting alkenyl succinic anhydride and a standard alkenyl succinic anhydride. Two infrared spectra were matched: 2900cm-1The left and right are stretching vibration peaks of methyl C-H, 2800cm-1About 1900cm of C-H stretching vibration peak of methylene-1The left and right are the stretching vibration peak of C ═ O, 1800cm-1Stretching vibration of C ═ CDynamic peak at 1500cm-1Is the C-H bending vibration peak, 1100cm-1Is the stretching vibration peak of C-O, 900cm-1The vicinity is a stretching vibration peak of ═ C-H.
Example 2
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 0.95g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 82%.
Example 3
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 3.80g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 84%.
Example 4
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the prepared heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 100kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 80%.
Example 5
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the prepared heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 300kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 85%.
Example 6
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the prepared heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 100r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 78%.
Example 7
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 300r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 83%.
Example 8
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 8 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 88%.
Example 9
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 12 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 86%.
Example 10
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 210 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 79%.
Example 11
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 230 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 86%.
Example 12
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 14 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 86%.
Example 13
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the prepared heteropoly acid catalyst in a reaction kettle, introducing nitrogen to evacuate air, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 18 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 87%.
Example 14
The heteropolyacid catalyst prepared by the method is used for preparing alkenyl succinic anhydride, and comprises the following steps:
weighing 20g of endo-octadecene and 20g of endo-hexadecene, weighing 15.3g of maleic anhydride and 1.90g of the prepared heteropoly acid catalyst, fully mixing the maleic anhydride and the prepared heteropoly acid catalyst in a reaction kettle, introducing no nitrogen, wherein the system pressure is 200kPa, the stirring speed is set to 200r/min, the temperature is gradually increased to 180 ℃, then the temperature is increased to 220 ℃ at the rate of 10 ℃ per hour, and the reaction is continued for 16 hours to obtain an alkenyl succinic anhydride solution, wherein the catalyst is recycled for 20 times, and the conversion rate of the alkenyl succinic anhydride reaches 75%.
For a clearer comparison of the experimental results, table 1 gives the results obtained under the conditions of the various influencing factors, as shown in the following table:
TABLE 1 different influencing factors of the alkenylsuccinic anhydride Synthesis reaction the results were obtained
With reference to examples 1 to 3, it can be seen that the influence of the amount of the heteropoly acid catalyst on the conversion rate of ASA synthesis: when the amount of the catalyst is reduced by one time according to the mass ratio of the catalyst to the total reactant, the conversion rate of the catalytic reaction is greatly reduced because the content of the catalyst is insufficient and the catalytic efficiency is low; when the amount of the catalyst is doubled according to the mass ratio of the catalyst to the total reactant, the conversion rate of the catalytic reaction is slightly reduced because the content of the catalyst is increased, the reaction rate of side reactions is increased, and the purity of the product is affected. The most suitable amount of catalyst for the catalytic reaction is 2% of the total reactant mass.
Combining examples 1, 4 and 5, it is known that the effect of different pressures of the catalytic reaction on the conversion of the synthesized ASA: the conversion rate of the catalytic reaction is greatly reduced along with the reduction of the system pressure; the catalytic conversion rate slightly decreases with increasing system pressure. The most suitable pressure for the catalytic reaction is 200 kPa.
With reference to examples 1, 6 and 7, it is possible to see the effect of different stirring speeds of the catalytic reaction on the conversion of the synthesized ASA: the catalytic reaction conversion rate is greatly reduced along with the reduction of the stirring rotating speed; with the increase of the stirring speed, the occurrence frequency of side reactions is increased, and the conversion rate of catalytic reactions is slightly reduced. The most suitable stirring speed of the catalytic reaction is 200 r/min.
Combining examples 1, 8 and 9, it is known that different rates of temperature increase after the catalytic reaction has been raised to 180 ℃ have an effect on the conversion of the synthesized ASA: the catalytic reaction conversion rate is basically kept unchanged along with the decrease of the temperature rising rate per hour, because the decrease of the temperature rising rate does not influence the reaching of the final temperature, and the slow temperature rising is favorable for controlling the occurrence of side reactions; the catalytic conversion decreases with increasing rate of temperature rise per hour, since a rapid temperature rise greatly increases the frequency of increased side reactions. The most suitable rate of temperature rise after the temperature rise of the catalytic reaction reaches 180 ℃ is 10 ℃ per hour.
With reference to examples 1, 10 and 11, it is known that the effect of different temperature conditions of the catalytic reaction on the conversion of the synthesized ASA: when the temperature of the catalytic reaction system is reduced, the conversion rate is greatly reduced, because the temperature at the moment can not reach the standard of the generation of a large amount of ASA; when the temperature of the catalytic reaction system is increased, the conversion rate is slightly reduced, because the temperature is too high, the occurrence frequency of side reactions is higher, and a large amount of byproducts are brought. The most suitable reaction temperature for the catalytic reaction is 220 ℃.
With reference to examples 1, 12 and 13, it is possible to see the effect of different reaction times of the catalytic reaction on the conversion of the synthesized ASA: when the reaction time of the catalytic reaction is reduced, part of reactants are not available for reaction, and the ASA conversion rate is reduced; when the reaction time of the catalytic reaction is increased, the reactants are completely reacted, and the excessive time can lead to the continuous increase of byproducts and the reduction of the conversion rate. The most suitable reaction time for the catalytic reaction is 16 h.
Combining examples 1 and 14, it is known that the gas atmosphere in the catalytic reaction system has an influence on the conversion rate of the synthesized ASA: when the catalytic reaction system is filled with air, the reactant can generate oxidation reaction with oxygen in the air at high temperature, so that byproducts are increased, and the conversion rate of synthesizing ASA is reduced; when the catalytic system is filled with nitrogen, the reactants are prevented from oxidation reaction, and the stability of the conversion rate of the synthesized ASA is ensured.
It should be noted that the number of times of using the catalyst in all the above cases is 20, and the influence on the conversion rate of the synthesized ASA is small, which indicates that the heteropoly acid catalyst has good using effect, can be recycled and can be reused in large quantities.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A method for preparing alkenyl succinic anhydride is characterized by comprising the following steps:
after the mixture of the mixed internal olefin and the maleic anhydride is added with a heteropoly acid catalyst, heating and reacting to generate alkenyl succinic anhydride; the mixed internal olefin is a mixture of internal hexadecene and internal octadecene.
2. The production method according to claim 1, wherein the heteropolyacid catalyst is one or a combination of two or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenotungstic acid, arsenomolybdic acid, borotungstic acid, boromolybdic acid, germanotungstic acid, germanomolybdic acid, phosphotungstomolybdic acid, silicotungstomolybdic acid, arsenotungomolybdic acid, borotungstomolybdic acid, and germanotungstomolybdic acid;
one or a combination of two or more of phosphotungstic acid, phosphomolybdic acid and phosphotungstomolybdic acid is preferable.
3. The production method according to claim 2, characterized in that a heteropoly acid supported on a carrier constitutes the heteropoly acid catalyst;
preferably, the carrier is one or a combination of more than two of alumina, silica, alumina-silica, titania, zeolite, kaolinite, clay, activated carbon and silicon carbide;
preferably, the heteropolyacid is supported on a silica body.
4. A production process according to claim 3, characterized in that, when the heteropoly acid is supported on the support, the support accounts for 0.1% to 90%, preferably 0.1% to 30% of the total weight of the heteropoly acid catalyst; more preferably 15% to 25%.
5. A preparation process according to any one of claims 2 to 4, wherein the heteropolyacid catalyst contains one or more of crystal water numbers of 0, 6, 10, 14, 22 and 36.
6. The production method according to claim 5, wherein the heteropoly acid catalyst is a solid powder.
7. The production method according to claim 5, wherein the heteropoly acid catalyst is produced by:
s1, mixing sodium tungstate, silicon dioxide, concentrated hydrochloric acid, concentrated phosphoric acid and distilled water, stirring uniformly, gradually heating to 50-90 ℃, stopping heating when the solid in the solution is completely dissolved and the color of the solution is changed into light yellow, and cooling the system to room temperature to obtain a solution A;
s2, adding a solvent to extract the solution A to obtain a solution B;
and S3, removing the solvent in the solution B, and drying and calcining to obtain a solid C, namely the heteropoly acid catalyst.
8. The production method according to claim 7, wherein the production method of the heteropoly acid catalyst further comprises:
s4, grinding the solid C into powder, and collecting the solid powder heteropoly acid catalyst.
9. The method according to claim 7, wherein the concentration of the concentrated hydrochloric acid is 10.0 wt.% to 38.0 wt.%, and the concentration of the concentrated phosphoric acid is 50.0 wt.% to 90.0 wt.%;
preferably, the molar ratio of the sodium tungstate to the silicon dioxide to the concentrated phosphoric acid is 15:1:1-1:1: 1;
preferably, the volume ratio of the concentrated hydrochloric acid to the distilled water is 1:5-1: 10;
preferably, the solvent is carbon tetrachloride, diethyl ether, 1, 2-dichloroethane, or ethanol;
preferably, the solution B in S3 is evaporated to remove the solvent;
preferably, the drying and calcining step described in S3 comprises: drying at 50-200 deg.c for 1-5 hr to constant weight, and calcining at 200-250 deg.c for 1-3 hr.
10. The preparation method according to claim 1, wherein the mass ratio of the endo-hexadecene to the endo-octadecene is 1: 1-4, more preferably, the mass ratio of the endo-hexadecene to the endo-octadecene is 1: 1;
preferably, the molar ratio of the maleic anhydride to the mixed internal olefin is 1: 1-4, more preferably, the molar ratio of the maleic anhydride to the mixed internal olefin is 1: 2;
preferably, the mass ratio of the heteropoly acid catalyst to the total reactant of the mixed internal olefin and the maleic anhydride is 1: 10-100, and more preferably, the mass ratio of the heteropoly acid catalyst to the total reactant of the mixed internal olefin and the maleic anhydride is 1: 50;
preferably, the heating temperature is 150-250 ℃; more preferably, the heating temperature is 200-220 ℃;
preferably, after the temperature of the reaction system reaches 180 ℃, the heating rate is 9-13 ℃ per hour; more preferably, the temperature rise rate is 10 ℃ per hour after the temperature of the reaction system reaches 180 ℃;
preferably, the pressure of the reaction system is 100kPa to 1000 kPa; more preferably, the pressure of the reaction system is 100kPa to 200 kPa;
preferably, the reaction time is 5-20 h; more preferably, the time of the catalytic reaction is 16-18 h;
preferably, stirring is carried out in the reaction process, and the stirring speed is 50-500 r/min; more preferably, the rotating speed of the stirring is 150-300 r/min;
preferably, the alkenylsuccinic anhydride preparation reaction is carried out in the absence of oxygen.
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| CN115124083A (en) * | 2022-07-27 | 2022-09-30 | 哈尔滨工业大学 | Keggin type heteropoly acid, preparation method thereof and application thereof in carbon reduction |
| CN116655564A (en) * | 2023-07-28 | 2023-08-29 | 山东奥赛新材料有限公司 | Alkenyl succinic anhydride, preparation method and application thereof in ASA sizing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113735805A (en) * | 2021-07-06 | 2021-12-03 | 上海昶法新材料有限公司 | Process for preparing alkenyl succinic anhydride |
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| CN116655564A (en) * | 2023-07-28 | 2023-08-29 | 山东奥赛新材料有限公司 | Alkenyl succinic anhydride, preparation method and application thereof in ASA sizing agent |
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