Isomerization reaction catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of isomerization reaction catalysts, in particular to an isomerization reaction catalyst and a preparation method and application thereof.Sodium metaaluminate, silica sol, sodium hydroxide and hexamethyleneimine are added into distilled water to be stirred and mixed to obtain a reaction mixture, the reaction mixture comprises SiO2, Al2O3, NaOH, HMI and H2O, the reactant mixture is crystallized to obtain a crude product, and the crude product is dried to obtain the isomerization reaction catalyst. Carrying out suction filtration, washing and drying on the crude product to obtain molecular sieve raw powder; the molecular sieve raw powder is roasted and then is subjected to ion exchange by using an ammonium nitrate solution, the isomerization reaction catalyst is obtained after continuous roasting, a proper internal olefin raw material is obtained by using the catalyst in cooperation with isomerization condition control, and ASA synthesized by the internal olefin is excellent in paper sizing performance.

Description

Technical Field

[0001] The invention relates to the technical field of isomerization reaction catalysts, in particular to an isomerization reaction catalyst and a preparation method and application thereof. Background Art

[0002] As a high-grade paper sizing agent, alkenyl succinic anhydride (ASA) has the characteristics of good compatibility with alkaline fillers or pigments, good paper strength, etc., and its sizing cost is low and the sizing maturation speed is fast, so it has good application prospects. Compared with traditional domestic rosin sizing agents, ASA sizing agents can protect the paper life longer and avoid the yellowing and brittleness of paper caused by acidity. Most of the developed countries abroad have completed the transition from acid sizing to neutral sizing agents, and the market share of ASA sizing agents has good prospects in China. In the process of sizing in paper pulp, ASA needs to be emulsified into a sizing liquid before sizing, so the papermaking industry has high requirements for its melting point, stability after emulsification, and water resistance of paper after sizing. ASA synthesized from long-chain α-olefins is solid at room temperature, so the industrial synthesis of ASA is mainly divided into two steps. α-olefins are subjected to isomerization reaction to prepare internal olefins, and internal olefins and maleic anhydride are used to synthesize alkenyl succinic anhydride. Its sizing performance is greatly affected by the structure of the olefin raw materials (chain length, double bond position and branching structure, etc.).

[0003] The catalyst manufacturing process of existing alpha-olefin isomerization is relatively complicated and the introduction of metal is relatively expensive or the use of dangerous raw materials is not suitable for industrial production. As the method of alpha-olefin isomerization to internal olefin disclosed in Chinese patent (publication number is CN101044105A), the final mixture formed by the clay of acid washing after the three alkyl aluminum and the salt of the VIII group transition metal are mixed is used as catalyst, and the catalyst in the invention uses trialkyl aluminum compound, and this material is very active and explodes when it meets water, and is more dangerous. In the method for preparing ASA raw material by alpha-olefin isomerization disclosed in Chinese patent (publication number is CN101044105A), the loaded metal catalyst used carries out isomerization reaction, and the loaded catalyst is that precious metals such as palladium, ruthenium, platinum, rhodium are loaded on carbon with developed pore structure, large specific surface area, and good strength, and the implementation difficulty is not high but relatively expensive and cannot be applied to industrial production. Summary of the invention

[0004] In order to solve the above problems, the present invention provides an isomerization reaction catalyst, which is used in combination with isomerization conditions to obtain a suitable internal olefin raw material, and the ASA synthesized from the internal olefin has excellent performance in paper sizing.

[0005] On one hand, the present invention provides an isomerization reaction catalyst, which at least comprises the following raw materials: sodium aluminate, silica sol, sodium hydroxide, hexamethyleneimine and distilled water.

[0006] On the other hand, the present invention provides a method for preparing an isomerization reaction catalyst, which comprises at least the following steps: adding sodium aluminate, silica sol, sodium hydroxide and hexamethyleneimine into distilled water, stirring and mixing to obtain a reaction mixture, wherein the reaction mixture comprises SiO2, Al2O3, NaOH, HMI and H2O; crystallizing the reactant mixture to obtain a crude product; filtering, washing and drying the crude product to obtain a molecular sieve raw powder; roasting the molecular sieve raw powder, performing ion exchange with an ammonium nitrate solution, and continuing roasting to obtain an isomerization reaction catalyst.

[0007] As a preferred technical solution, the molar ratio of SiO2, Al2O3, NaOH, HMI and H2O in the reaction mixture is 1:(0.03-0.05):(0.2-0.5):(0.6-1.0):(10-30).

[0008] As a preferred technical solution, the method for preparing the reaction mixture is: adding sodium hydroxide and sodium aluminate to distilled water to obtain a mixed aqueous solution, adding hexamethyleneimine to the mixed aqueous solution at 15-35° C., adding silica sol at a stirring speed of 200-500 r / min and stirring for 1-3 hours to obtain a reaction mixture.

[0009] As a preferred technical solution, the crystallization temperature is 150-170° C., the crystallization time is 64-81 h, and the crystallization stirring speed is 200-300 r / min.

[0010] As a preferred technical solution, the concentration of the ammonium nitrate solution is 1.0-2.0 mol / L, preferably 1.4-1.7 mol / L.

[0011] As a preferred technical solution, the ion exchange temperature is 70-90°C, and the ion exchange time is 12-18h.

[0012] As a preferred technical solution, the calcination temperature is 500-600°C and the calcination time is 3-6h.

[0013] As a preferred technical solution, the isomerization reaction catalyst has a silicon-to-aluminum ratio of 8-15 and a specific surface area of ​​390-420 m 2 / g, and the average pore size is 8-15nm.

[0014] The present invention optimizes the raw material ratio of the isomerization reaction catalyst, coordinates the crystallization conditions and controls the ion exchange conditions, so that the obtained isomerization reaction catalyst has excellent catalytic performance for subsequent isomerization reactions, effectively reduces the polymerization and blockage of olefins, and further improves the service life of the catalyst. In particular, the molar ratio of SiO2, Al2O3, NaOH, HMI, and H2O in the reaction mixture is controlled to be 1: (0.03-0.05): (0.2-0.5): (0.6-1.0): (10-30), and under specific crystallization conditions and ion exchange conditions, the provided isomerization reaction catalyst has a mild reaction and a high degree of isomerization during the catalytic isomerization reaction, and the isomerization reaction has a high selectivity. The analysis reason may be: by comprehensively controlling the molar ratio of each raw material and the reaction conditions, the synthesized isomerization reaction catalyst has a special pore structure and a suitable pore size, has a strong active center and a low acid center density, and improves its catalytic performance for olefin isomerization reactions. The preparation method of the isomerization reaction catalyst provided by the present invention is simple, has low implementation difficulty and low cost, and is conducive to realizing industrial production.

[0015] The third aspect of the present invention provides an application of an isomerization reaction catalyst for preparing alkenyl succinic anhydride.

[0016] As a preferred technical solution, the method for preparing alkenyl succinic anhydride comprises at least the following steps: α-olefin is contacted with an isomerization reaction catalyst to carry out isomerization reaction to prepare internal olefin, and internal olefin is reacted with maleic anhydride to obtain alkenyl succinic anhydride.

[0017] As a preferred technical solution, the preparation method of alkenyl succinic anhydride is as follows: an isomerization reaction catalyst is loaded into a fixed bed reactor and nitrogen protection is connected; α-olefin is preheated in a preheater and then enters the fixed bed reactor from the top to contact with the isomerization reaction catalyst for isomerization reaction; after the reaction is completed, the material is discharged from the bottom of the fixed bed reactor and enters a condenser for cooling to obtain internal olefins; the internal olefins and maleic anhydride are added to a reactor, nitrogen is replaced, and a synthesis reaction is performed to obtain a crude product; the crude product is distilled under negative pressure to separate and recover the olefins, and the alkenyl succinic anhydride is obtained after filtration.

[0018] As a preferred technical solution, the preheating temperature of the preheater is 170-175°C.

[0019] As a preferred technical solution, the structural formula of the α-olefin is C n H 2n , n=12-20.

[0020] Preferably, the α-olefin is α-18 olefin.

[0021] As a preferred technical solution, the temperature of the isomerization reaction is 150-200°C, preferably 170-180°C.

[0022] As a preferred technical solution, the mass space velocity of the α-olefin is 0.2-0.5h -1 .

[0023] As a preferred technical solution, the mass ratio of maleic anhydride to internal olefin is (3-8):1, preferably (4-6):1.

[0024] As a preferred technical solution, the temperature of the synthesis reaction is 160-200°C, and the time of the synthesis reaction is 18-24h.

[0025] The present invention uses a fixed bed reactor filled with an isomerization reaction catalyst to carry out an isomerization reaction, thereby realizing continuous operation of the reaction device, having high reaction selectivity, effectively inhibiting the self-polymerization or cross-polymerization reaction of olefins in the isomerization reaction, and having higher safety. Specifically, the present invention controls the content of dimers and α-olefins in the internal olefins to a suitable content by controlling the isomerization reaction conditions and the synthesis reaction conditions, thereby ensuring the subsequent sizing application effect.

[0026] The present invention avoids the use of distillation separation and purification steps during the isomerization reaction process, thereby improving the overall yield and reducing energy consumption and equipment investment costs.

[0027] Beneficial Effects

[0028] 1. The present invention provides an isomerization reaction catalyst. The catalyst is used in combination with isomerization conditions to obtain a suitable internal olefin raw material. The ASA synthesized from the internal olefin has excellent performance in paper sizing.

[0029] 2. The present invention optimizes the raw material ratio of the isomerization reaction catalyst, coordinates the crystallization conditions and controls the ion exchange conditions, so that the obtained isomerization reaction catalyst has excellent catalytic performance for subsequent isomerization reactions, effectively reduces the polymerization and blockage of olefins, and further improves the service life of the catalyst.

[0030] 3. The present invention controls the molar ratio of SiO2, Al2O3, NaOH, HMI and H2O in the reaction mixture to be 1:(0.03-0.05):(0.2-0.5):(0.6-1.0):(10-30), and under specific crystallization conditions and ion exchange conditions, the provided isomerization reaction catalyst has a mild reaction and a high degree of isomerization during the catalytic isomerization reaction, and the isomerization reaction has high selectivity.

[0031] 4. The present invention adopts a fixed bed reactor filled with an isomerization reaction catalyst to carry out the isomerization reaction, thereby realizing continuous operation of the reaction device, having high reaction selectivity, effectively inhibiting the self-polymerization or cross-polymerization reaction of olefins in the isomerization reaction, and having higher safety.

[0032] 5. The present invention controls the isomerization reaction conditions and the synthesis reaction conditions to control the dimer and α-olefin contents in the internal olefins to a suitable content, thereby ensuring the subsequent sizing application effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the XRD diffraction pattern of the isomerization reaction catalyst provided in Example 1 of the present invention.

[0034] Figure 2 This is a pore size distribution diagram of the isomerization reaction catalyst provided in Example 1 of the present invention.

[0035] Figure 3 This is a scanning electron microscope (SEM) characterization image of the isomerization reaction catalyst provided in Example 1 of the present invention.

[0036] Figure 4 This is an adsorption test curve diagram of the isomerization reaction catalyst provided in Example 1 of the present invention.

[0037] Figure 5 This is a schematic diagram of the structure of the isomerization reaction device used in Example 1 of the present invention, in which 1. α-18 olefin feed tank; 2. metering pump; 3. preheater; 4. fixed bed reactor; 5. condenser; and 7. product receiving bottle. DETAILED DESCRIPTION

[0038] Example 1

[0039] Example 1 of the present invention provides an isomerization reaction catalyst, comprising the following raw materials: sodium aluminate, silica sol, sodium hydroxide, hexamethyleneimine, and distilled water.

[0040] On the other hand, Example 1 of the present invention provides a method for preparing an isomerization reaction catalyst, comprising the following steps: adding sodium hydroxide and sodium aluminate to distilled water to obtain a mixed aqueous solution, adding hexamethyleneimine to the mixed aqueous solution at 25±2°C, adding silica sol and stirring for 2h at a stirring speed of 400r / min to obtain a reaction mixture. The reaction mixture includes SiO2, Al2O3, NaOH, HMI, and H2O, and the reactant mixture is placed in a stainless steel autoclave lined with polytetrafluoroethylene, and crystallized at 250r / min and 160°C for 72h in a N2 atmosphere to obtain a crude product, and the crude product is filtered, washed, and dried to obtain a molecular sieve raw powder; the molecular sieve raw powder is placed in a muffle furnace, and roasted at 550°C for 6h in an air atmosphere, and then ion exchange is performed with a 1.5mol / L ammonium nitrate solution at 80°C for 15h, and the isomerization reaction catalyst is obtained after being placed in a muffle furnace and continued to be roasted at 550°C for 3h.

[0041] The molar ratio of SiO2, Al2O3, NaOH, HMI and H2O in the reaction mixture is 1:0.033:0.40:0.7:25.

[0042] The isomerization reaction catalyst is a white powder with a silicon-aluminum ratio of 15 and a specific surface area of ​​402.3114 m 2 / g, and the average pore size is 10.0nm.

[0043] Example 2

[0044] Example 2 of the present invention provides an isomerization reaction catalyst, comprising the following raw materials: sodium aluminate, silica sol, sodium hydroxide, hexamethyleneimine, and distilled water.

[0045] On the other hand, Example 2 of the present invention provides a method for preparing an isomerization reaction catalyst, comprising the following steps: adding sodium hydroxide and sodium aluminate to distilled water to obtain a mixed aqueous solution, adding hexamethyleneimine to the mixed aqueous solution at 25±2°C, adding silica sol and stirring for 2h at a stirring speed of 400r / min to obtain a reaction mixture. The reactant mixture is placed in a stainless steel autoclave lined with polytetrafluoroethylene, and crystallized at 250r / min and 150°C for 80h in a N2 atmosphere to obtain a crude product, and the crude product is filtered, washed, and dried to obtain a molecular sieve raw powder; the molecular sieve raw powder is placed in a muffle furnace, and roasted at 550°C for 6h in an air atmosphere, and then ion exchange is performed with a 1.5mol / L ammonium nitrate solution at 80°C for 12h, and the isomerization reaction catalyst is obtained after being placed in a muffle furnace and continued to be roasted at 550°C for 3h.

[0046] The molar ratio of SiO2, Al2O3, NaOH, HMI and H2O in the reaction mixture is 1:0.033:0.20:0.7:20.

[0047] The isomerization reaction catalyst is a white powder with a silicon-aluminum ratio of 15 and a specific surface area of ​​392.021 m 2 / g, and the average pore size is 12.4nm.

[0048] Example 3

[0049] Example 3 of the present invention provides an isomerization reaction catalyst, comprising the following raw materials: sodium aluminate, silica sol, sodium hydroxide, hexamethyleneimine, and distilled water.

[0050] On the other hand, Example 3 of the present invention provides a method for preparing an isomerization reaction catalyst, comprising the following steps: adding sodium hydroxide and sodium aluminate to distilled water to obtain a mixed aqueous solution, adding hexamethyleneimine to the mixed aqueous solution at 25±2°C, adding silica sol and stirring for 2h at a stirring speed of 400r / min to obtain a reaction mixture. The reactant mixture is placed in a stainless steel autoclave lined with polytetrafluoroethylene, and crystallized at 250r / min and 160°C for 70h in a N2 atmosphere to obtain a crude product, and the crude product is filtered, washed, and dried to obtain a molecular sieve raw powder; the molecular sieve raw powder is placed in a muffle furnace, roasted at 550°C for 6h in an air atmosphere, and then ion exchanged with a 1.5mol / L ammonium nitrate solution at 80°C for 13h, and then placed in a muffle furnace and continued to be roasted at 550°C for 3h to obtain an isomerization reaction catalyst.

[0051] The molar ratio of SiO2, Al2O3, NaOH, HMI and H2O in the reaction mixture is 1:0.05:0.40:1.0:25.

[0052] The isomerization reaction catalyst is a white powder with a silicon-aluminum ratio of 10 and a specific surface area of ​​418.530 m 2 / g, and the average pore size is 9.4nm.

[0053] Example 4

[0054] Example 4 of the present invention provides an isomerization reaction catalyst, comprising the following raw materials: sodium aluminate, silica sol, sodium hydroxide, hexamethyleneimine, and distilled water.

[0055] Embodiment 4 of the present invention provides a method for preparing an isomerization reaction catalyst, comprising the following steps: adding sodium hydroxide and sodium aluminate to distilled water to obtain a mixed aqueous solution, adding hexamethyleneimine to the mixed aqueous solution at 25±2°C, adding silica sol and stirring for 2h at a stirring speed of 400r / min to obtain a reaction mixture. The reactant mixture is placed in a stainless steel autoclave lined with polytetrafluoroethylene, and crystallized at 250r / min and 140°C for 50h in a N2 atmosphere to obtain a crude product, and the crude product is filtered, washed, and dried to obtain a molecular sieve raw powder; the molecular sieve raw powder is placed in a muffle furnace, and roasted at 550°C for 6h in an air atmosphere, and then ion exchange is performed with a 1.5mol / L ammonium nitrate solution at 80°C for 15h, and the isomerization reaction catalyst is obtained after being placed in a muffle furnace and continued to be roasted at 550°C for 3h.

[0056] The molar ratio of SiO2, Al2O3, NaOH, HMI and H2O in the reaction mixture is 1:0.033:0.40:0.7:25.

[0057] The isomerization reaction catalyst is a white powder with a silicon-aluminum ratio of 15 and a specific surface area of ​​278.233 m 2 / g, and the average pore size is 20.6nm.

[0058] Example 5

[0059] Example 5 of the present invention provides an isomerization reaction catalyst, comprising the following raw materials: sodium aluminate, silica sol, sodium hydroxide, hexamethyleneimine, and distilled water.

[0060] Embodiment 5 of the present invention provides a method for preparing an isomerization reaction catalyst, comprising the following steps: adding sodium hydroxide and sodium aluminate to distilled water to obtain a mixed aqueous solution, adding hexamethyleneimine to the mixed aqueous solution at 25±2°C, adding silica sol and stirring for 2h at a stirring speed of 400r / min to obtain a reaction mixture. The reactant mixture is placed in a stainless steel autoclave lined with polytetrafluoroethylene, and crystallized at 250r / min and 160°C for 72h in a N2 atmosphere to obtain a crude product, and the crude product is filtered, washed, and dried to obtain a molecular sieve raw powder; the molecular sieve raw powder is placed in a muffle furnace, roasted at 550°C for 6h in an air atmosphere, and then ion exchanged with a 1.5mol / L ammonium nitrate solution at 80°C for 10h, and then placed in a muffle furnace and continued to be roasted at 550°C for 3h to obtain an isomerization reaction catalyst.

[0061] The molar ratio of SiO2, Al2O3, NaOH, HMI and H2O in the reaction mixture is 1:0.033:0.40:0.7:25.

[0062] The isomerization reaction catalyst is a white powder with a silicon-aluminum ratio of 15 and a specific surface area of ​​352.417 m 2 / g, and the average pore size is 16.7nm.

[0063] Application Example 1

[0064] Application Example 1 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device is used to synthesize isooctadecene product 1, 100 g of isomerization reaction catalyst (Example 1) is loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature is 175° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 30 g / h (mass space velocity 0.3 h -1 ) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 1) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 1 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 1 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is distilled and separated under negative pressure to recover olefins, and filtrated to obtain alkenyl succinic anhydride 1.

[0065] Application Example 2

[0066] Application Example 2 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device is used to synthesize isooctadecene product 2, 100 g of isomerization reaction catalyst (Example 1) is loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature is 175° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 20 g / h (mass space velocity 0.2 h -1 ) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 1) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 2 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 2 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is separated and olefins are recovered by distillation under negative pressure, and alkenyl succinic anhydride 2 is obtained after filtration.

[0067] Application Example 3

[0068] Application Example 3 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device is used to synthesize isooctadecene product 3, 100 g of isomerization reaction catalyst (Example 1) is loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature is 180° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 50 g / h (mass space velocity 0.5 h -1 ) is heated to 180°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 1) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 3 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 3 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is distilled and separated under negative pressure to recover olefins, and filtered to obtain alkenyl succinic anhydride 3.

[0069] Application Example 4

[0070] Application Example 4 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device is used to synthesize isooctadecene product 4, 100 g of isomerization reaction catalyst (Example 1) is loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature is 180° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 70 g / h (mass space velocity 0.7 h -1 ) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 1) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 4 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 4 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is separated and olefins are recovered by distillation under negative pressure, and alkenyl succinic anhydride 4 is obtained after filtration.

[0071] Application Example 5

[0072] Application Example 5 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4, an isomerization reaction device is used to synthesize isooctadecene product 5, 100 g of isomerization reaction catalyst (Example 1) is filled into a fixed bed reactor 4, the fixed bed reactor layer temperature is 200° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 40 g / h (mass space velocity 0.4 h -1 ) is heated to 200°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 1) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 5 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 5 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is separated and olefins are recovered by distillation under negative pressure, and alkenyl succinic anhydride 5 is obtained after filtration.

[0073] Application Example 6

[0074] Application Example 6 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device is used to synthesize isooctadecene product 1, 100 g of isomerization reaction catalyst (Example 1) is loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature is 175° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 30 g / h (mass space velocity 0.3 h -1 ) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 1) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 1 which is collected in a product receiving bottle 6. 400g of the isooctadecene product 1 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 200°C for 20h to obtain a crude product. The crude product is distilled and separated under negative pressure to recover olefins, and filtered to obtain alkenyl succinic anhydride 6.

[0075] Application Example 7

[0076] Application Example 7 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device is used to synthesize isooctadecene product 1, 100 g of isomerization reaction catalyst (Example 1) is loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature is 175° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 30 g / h (mass space velocity 0.3 h -1) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 1) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 1 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 1 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 220°C for 18h to obtain a crude product. The crude product is separated and olefins are recovered by distillation under negative pressure, and alkenyl succinic anhydride 7 is obtained after filtration.

[0077] Application Example 8

[0078] Application Example 8 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device was used to synthesize isooctadecene product 8, 100 g of isomerization reaction catalyst (Example 2) was loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature was 175° C., and nitrogen protection was connected; the α-18 olefin in the α-18 olefin feed tank 1 was pumped through a metering pump 2 at a flow rate of 30 g / h (mass space velocity 0.3 h -1 ) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 2) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 8 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 8 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is separated and olefins are recovered by distillation under negative pressure, and alkenyl succinic anhydride 8 is obtained after filtration.

[0079] Application Example 9

[0080] Application Example 9 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device was used to synthesize isooctadecene product 9, 100 g of isomerization reaction catalyst (Example 3) was loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature was 175° C., and nitrogen protection was connected; the α-18 olefin in the α-18 olefin feed tank 1 was pumped through a metering pump 2 at a flow rate of 30 g / h (mass space velocity 0.3 h -1) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 3) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 9 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 9 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is separated and olefins are recovered by distillation under negative pressure, and alkenyl succinic anhydride 9 is obtained after filtration.

[0081] Application Example 10

[0082] Application Example 10 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device is used to synthesize isooctadecene product 10, 100 g of isomerization reaction catalyst (Example 4) is loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature is 175° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 30 g / h (mass space velocity 0.3 h -1 ) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 4) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 10 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 10 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is separated and olefins are recovered by distillation under negative pressure, and alkenyl succinic anhydride 10 is obtained after filtration.

[0083] Application Example 11

[0084] Application Example 11 of the present invention provides a method for preparing alkenyl succinic anhydride, comprising the following steps: Figure 4 , an isomerization reaction device is used to synthesize isooctadecene product 1, 100 g of isomerization reaction catalyst (Example 5) is loaded into a fixed bed reactor 4, the fixed bed reactor layer temperature is 175° C., and nitrogen protection is connected; the α-18 olefin in the α-18 olefin feed tank 1 is pumped through a metering pump 2 at a flow rate of 30 g / h (mass space velocity 0.3 h -1) is heated to 175°C in a preheater 3, and enters from the top of a fixed bed reactor 4 to contact with an isomerization reaction catalyst (Example 5) for isomerization reaction. After the reaction is completed, the material is discharged from the bottom of the fixed bed reactor 4, enters a condenser 4 and is cooled to 25±2°C to obtain an isooctadecene product 11 which is collected in a product receiving bottle 6. 500g of the isooctadecene product 11 and 100g of maleic anhydride are added to a reactor, replaced with nitrogen, and a synthesis reaction is carried out at 180°C for 20h to obtain a crude product. The crude product is separated and olefins are recovered by distillation under negative pressure, and alkenyl succinic anhydride 11 is obtained after filtration.

[0085] Performance Testing

[0086] 1. The isooctadecene products 1-5 and the isooctadecene products 8-11 were subjected to nuclear magnetic resonance and gas phase analysis. The analysis results are shown in Table 1.

[0087] Table 1

[0088]

[0089]

[0090] 2. The yield of alkenyl succinic anhydride 1-11 was calculated based on maleic anhydride, and the purity of alkenyl succinic anhydride 1-11 was tested (GCMS area normalization method). If the purity was > 99%, the product purity was recorded as "qualified", otherwise it was recorded as unqualified. The test results are shown in Table 2.

[0091] Table 2

[0092] Example Yield / % purity / % Alkenyl succinic anhydride 1 97.8 qualified Alkenyl succinic anhydride 2 97.5 qualified Alkenyl succinic anhydride 3 97.2 qualified Alkenyl succinic anhydride 4 96.5 qualified Alkenyl succinic anhydride 5 95.4 qualified Alkenyl succinic anhydride 6 95.7 qualified Alkenyl succinic anhydride 7 90.5 qualified Alkenyl succinic anhydride 8 97.3 qualified Alkenyl succinic anhydride 9 96.1 qualified Alkenyl succinic anhydride 10 95.2 qualified Alkenyl succinic anhydride 11 95.7 qualified

[0093] 3. Add 0.25g of alkenyl succinic anhydride 1-11 and 50g of gelatinized cationic starch (model YL04M, Guangdong Hongxin Biotechnology Co., Ltd.) into a high-speed mixer at 5°C, stir at high speed (9000rpm) and emulsify for 2min to obtain ASA emulsion. Add ASA emulsion to pulp at an amount of 1wt%, and add retention aid (polyacrylamide, Jiangsu Fumiao Technology Co., Ltd., model 3970DG) at 2wt%, and make sheets with a basis weight of 70g / m 2 , the sizing degree of the hand sheet was determined (using the Cobb value method, tested according to GB / T 461.3-2005). The test results are shown in Table 3.

[0094] Table 3

[0095] Example Cobb value Alkenyl succinic anhydride 1 5.7 Alkenyl succinic anhydride 2 6.0 Alkenyl succinic anhydride 3 7.1 Alkenyl succinic anhydride 4 9.7 Alkenyl succinic anhydride 5 9.4 Alkenyl succinic anhydride 6 7.2 Alkenyl succinic anhydride 7 8.5 Alkenyl succinic anhydride 8 6.8 Alkenyl succinic anhydride 9 8.3 Alkenyl succinic anhydride 10 12.5 Alkenyl succinic anhydride 11 11.2

Claims

1. An isomerization reaction catalyst, characterized in that: The method comprises at least the following raw materials: sodium aluminate, silica sol, sodium hydroxide, hexamethyleneimine and distilled water.

2. A method for preparing an isomerization reaction catalyst according to claim 1, characterized in that: The method comprises at least the following steps: adding sodium aluminate, silica sol, sodium hydroxide and hexamethyleneimine into distilled water, stirring and mixing to obtain a reaction mixture, wherein the reaction mixture comprises SiO2, Al2O3, NaOH, HMI and H2O; crystallizing the reaction mixture to obtain a crude product; filtering, washing and drying the crude product to obtain molecular sieve raw powder; calcining the molecular sieve raw powder, performing ion exchange with ammonium nitrate solution, and continuing calcination to obtain an isomerization reaction catalyst.

3. The method for preparing an isomerization reaction catalyst according to claim 2, characterized in that: The molar ratio of SiO2, Al2O3, NaOH, HMI and H2O in the reaction mixture is 1:(0.03-0.05):(0.2-0.5):(0.6-1.0):(10-30).

4. The method for preparing an isomerization reaction catalyst according to claim 3, characterized in that: The crystallization temperature is 150-170° C., the crystallization time is 64-81 hours, and the crystallization stirring speed is 200-300 r / min.

5. The method for preparing an isomerization reaction catalyst according to claim 4, characterized in that: The concentration of the ammonium nitrate solution is 1.0-2.0 mol / L.

6. The method for preparing an isomerization reaction catalyst according to claim 5, characterized in that: The temperature of the ion exchange is 70-90° C., and the time of the ion exchange is 12-18 hours.

7. The method for preparing an isomerization reaction catalyst according to claim 6, characterized in that: The calcination temperature is 500-600° C., and the calcination time is 3-6 hours.

8. Use of the isomerization reaction catalyst according to claim 1, characterized in that: Used in the preparation of alkenyl succinic anhydride.

9. The use of the isomerization reaction catalyst according to claim 8, characterized in that: The method for preparing alkenyl succinic anhydride comprises at least the following steps: α-olefin is contacted with an isomerization reaction catalyst to carry out isomerization reaction to prepare internal olefin, and internal olefin is subjected to synthesis reaction with maleic anhydride to obtain alkenyl succinic anhydride.

10. The use of the isomerization reaction catalyst according to claim 8, characterized in that: The temperature of the isomerization reaction is 150-200°C.

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