Production method of trans-pentadiene

Abstract

The invention discloses a production method of trans-pentadiene. The method comprises the following steps: by taking cis-pentadiene as a reaction raw material, reacting in the presence of a solid-phase catalyst to generate trans-pentadiene; the solid-phase catalyst is a ZSM-5 molecular sieve, and the molecular sieve is a prism interpenetrating body formed by vertically crossing two straight hexagonal prisms. According to the method provided by the invention, the cis-pentadiene is contacted with the solid-phase catalyst for reaction, and the method has the characteristics of simplicity in operation, convenience in catalyst recovery and high yield of the trans-pentadiene product.

Description

Technical Field

[0001] The present invention relates to the field of catalytic technology, and more particularly to a method for producing trans-pentadiene. Background Art

[0002] C5 resources are by-product fractions of petroleum catalytic cracking and ethylene industry, mainly containing isopentadiene (PD), cyclopentadiene (CPD) and its dimer dicyclopentadiene (DCPD), which are the raw materials for synthesizing methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride. For some chemical reaction processes, high-purity cis- or trans-pentadiene is required as a raw material to obtain high-purity trans-pentadiene.

[0003] CN111978142A discloses a method for isomerizing cis-olefins to trans-olefins, wherein a palladium / copper catalyst is added to a reactor, an organic solvent is added, and the reaction is carried out under a hydrogen atmosphere to obtain trans-olefins. CN103145522A also discloses a method for isomerizing cis-pentadiene. The method uses [Co(CN) x [EN] -(x-2) and NaBH 4 The complex is used as a catalyst to isomerize cis-pentadiene to generate trans-pentadiene at a conversion rate of >99%, and the selectivity of the target product is also >99%.

[0004] The above methods use metal and homogeneous catalysts, the catalyst recovery is very difficult, the product and the catalyst cannot be separated, the separation steps are cumbersome, and no solid acid and molecular sieve are used as catalysts. Summary of the invention

[0005] In order to overcome the problems of the prior art that homogeneous catalysts are used, resulting in difficulty in separating products and low yield of trans-pentadiene, the present invention provides a method for producing trans-pentadiene. The method is characterized by simple operation, convenient catalyst recovery, and high yield of the trans-pentadiene product by contacting cis-pentadiene with a solid phase catalyst to react.

[0006] In order to achieve the above-mentioned purpose, the present invention provides a method for producing trans-pentadiene, comprising: taking cis-pentadiene as a reaction raw material, reacting in the presence of a solid phase catalyst to produce trans-pentadiene; the solid phase catalyst is a ZSM-5 molecular sieve, and the molecular sieve is a prismatic intercalation body formed by two right hexagonal prisms vertically crossing each other.

[0007] Furthermore, the cis-pentadiene is C5 cis-piperylene. Preferably, the mass content of cis-pentadiene in the cis-pentadiene raw material is 10%-100%.

[0008] Furthermore, the reaction conditions are: reaction temperature is 200°C-600°C, reaction pressure is 0-0.5MPa, liquid phase mass space velocity is 0.1-10h -1 .

[0009] Furthermore, the reaction conditions are: reaction temperature is 250°C-500°C, reaction pressure is 0.01-0.2MPa, liquid phase mass space velocity is 0.5-5h -1 .

[0010] According to a preferred embodiment of the present invention, after the reaction is completed, the solid phase catalyst and the product can be separated by filtration, centrifugation, etc.

[0011] Furthermore, in the prismatic interpenetrating body, each of the two right hexagonal prisms has two relatively large sides and four relatively small sides, the two relatively large sides are parallel, and there are two relatively small sides between the two relatively large sides; in the prismatic interpenetrating body, the relatively large sides of the two right hexagonal prisms are perpendicular to and penetrate each other, and the two adjacent relatively small sides of the two right hexagonal prisms are in the same projection direction.

[0012] Furthermore, the straight hexagonal prism has two bottom surfaces, both of which are hexagonal.

[0013] Furthermore, the height h of the right hexagonal prism is 2-4 μm.

[0014] Furthermore, a distance a between two relatively larger side surfaces of the right hexagonal prism is 1-2 μm.

[0015] Furthermore, the length b of the bottom edge of the relatively larger side of the right hexagonal prism is 1.5-3 times that of a.

[0016] Furthermore, the prismatic interpenetrating body is a prismatic interpenetrating body formed by two straight hexagonal prisms intersecting in a cross shape.

[0017] Furthermore, the atomic molar ratio of silicon to aluminum Si / Al of the ZSM-5 molecular sieve is 20-∞.

[0018] Furthermore, the preparation method of the ZSM-5 molecular sieve comprises the following steps:

[0019] A molecular sieve gel precursor is obtained by mixing a silicon source, an aluminum source, an additive, a template and water, and then added into an integrated high-gravity device for aging and crystallization together with a copolymer, pressurized and rotated under high gravity, and cycled. After the end, aging is performed, and then crystallization is performed under secondary pressurization conditions to obtain the ZSM-5 molecular sieve.

[0020] Furthermore, the molecular sieve gel precursor is prepared by preparing solution A with silicon source, template and water, preparing solution B with aluminum source, additive and water, and mixing solution A and solution B to obtain the molecular sieve gel precursor.

[0021] Furthermore, in the solution A, the molar ratio of silicon source, template and water, i.e. SiO 2 :Template agent:H 2 O is 1:0.1-0.6:5-1000; in the solution B, the molar ratio of aluminum source, additive and water is Si / Al=0.5-∞, additive: Al=0.01-50, H 2 O:Al=5-500.

[0022] Furthermore, the silicon source is at least one of silica sol, tetraethyl orthosilicate, amorphous silicon oxide, and silicate, and the aluminum source is at least one of aluminum sulfate 18hydrate, aluminum isopropoxide, aluminate, and aluminate.

[0023] Furthermore, the template agent is at least one of n-propylamine, n-butylamine, n-hexylamine, methylamine, ethylamine, ethylenediamine, butyrolactone, valerolactone, and caprolactone.

[0024] Furthermore, the additive is at least one of urea, diethanolamine, ammonium chloride and ammonia water.

[0025] Furthermore, the molecular sieve gel precursor used needs to be passed into an integrated high gravity device for aging and crystallization for circulation, and the number of cycles is at least 3 times, preferably 3-8 times.

[0026] Furthermore, each cycle time is 5-120 min, preferably 10-60 min.

[0027] Furthermore, the supergravity rotation speed during circulation is 500-5000 rpm, preferably 1000-3000 rpm.

[0028] Furthermore, after the molecular sieve gel precursor is passed into the integrated ultra-gravity device for aging and crystallization, pressure needs to be added during the circulation process.

[0029] Furthermore, the pressurization pressure is 0.01-10 MPa, preferably 0.05-8 MPa.

[0030] Furthermore, the copolymer includes at least one of a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer.

[0031] Further, the copolymer is preferably selected from at least one of P123, polystyrene-b-polymethyl methacrylate (PS-b-PMMA), and polybutadiene-styrene copolymer; wherein the molecular weight of polystyrene-b-polymethyl methacrylate (PS-b-PMMA) is 7500-50000; optionally, the polybutadiene-styrene copolymer is formed by copolymerization of styrene and butadiene, and the molecular weight of the polybutadiene-styrene copolymer is 10000-50000.

[0032] Furthermore, the copolymer and the silicon source are SiO 2 The molar ratio is 0.05-10, preferably 0.2-10.

[0033] Furthermore, the aging time is 24-96 hours. The aging is carried out under pressure and high gravity in an integrated high gravity device for aging and crystallization.

[0034] Furthermore, the increased pressure of the secondary pressurization is 0.01-10 MPa, preferably 0.1-8 MPa. The secondary pressurization is to increase the pressure on the basis of the first pressurization.

[0035] Furthermore, the crystallization conditions are: a crystallization temperature of 100-200° C., a crystallization time of 1-96 hours, and the crystallization is performed under secondary pressurization and supergravity in an integrated supergravity device for aging and crystallization.

[0036] Furthermore, the hypergravity level in the aging and crystallization integrated hypergravity device is 10g-600g.

[0037] Furthermore, after the crystallization, conventional washing and drying can be used to obtain the molecular sieve.

[0038] The solid phase molecular sieve provided by the present invention has a new morphological feature, is a prismatic intercalation body, and can be used in the reaction of synthesizing trans-pentadiene from cis-pentadiene, solving the problems of homogeneous catalysis in the prior art, high reaction temperature, and difficulty in separating the catalyst and the product. The method of the present invention is simple to operate, convenient for catalyst recovery, and high yield of trans-pentadiene product by contacting the reaction raw materials with the solid phase catalyst to react. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a SEM photo of the molecular sieve obtained in Example 1;

[0040] Figure 2 This is a SEM photo of the molecular sieve obtained in Comparative Example 1;

[0041] Figure 3 The XRD diffraction spectrum of the molecular sieve obtained in Example 1 is shown in FIG. DETAILED DESCRIPTION

[0042] The following examples will further illustrate the molecular sieve synthesis method provided by the present invention, but the protection scope of the present invention is not limited to these examples.

[0043] In the present invention, the scanning electron microscope (SEM) images of the samples were taken on a Hitachi S-4800II scanning electron microscope.

[0044] In the present invention, the XRD test conditions are as follows: the molecular sieve crystal phase analysis is performed using a Japanese Rigaku-Ultima X-ray diffractometer, CuKα radiation, wavelength λ=0.15432nm, the X-ray diffraction pattern scanning range 2θ is 5-50°, and the scanning speed is 10° / min.

[0045] [Example 1]

[0046] The silicon source is silica sol, the aluminum source is sodium aluminate, the template agent is n-propylamine, the additive is diethanolamine, and the copolymer is P123. 2 :0.4n-propylamine:500H 2 O to prepare solution A, Al 2 O 3 :0.2Diethanolamine:300H 2 Solution B (Si / Al molar ratio of 50) was prepared by slowly adding the above solution B into solution A. The molecular sieve gel precursor formed was introduced into an integrated ultra-gravity device for aging and crystallization, with a molar ratio of 0.2P123:SiO 2 , add copolymer P123, adjust the supergravity level to 100g, supergravity speed to 2000rpm, cycle 3 times, each cycle time is 20min, the pressure is added to 0.3MPa, after aging for 72 hours, pressurize 0.4MPa again, crystallize at 150℃ for 24h, wash and dry after crystallization to obtain molecular sieve, the morphology is shown Figure 1 ,pass Figure 1 It can be seen that the prismatic intercalation body morphology is presented, the height h of the straight hexagonal prism in the prismatic intercalation body is 2-4 μm, the distance a between the two relatively larger sides of the straight hexagonal prism is 1-2 μm, and the length b of the bottom edge in the relatively larger side of the straight hexagonal prism is 1.5-3 times of a. The XRD diffraction pattern of the molecular sieve is shown in Figure 3 ,Depend on Figure 3 It can be known to be ZSM-5 molecular sieve.

[0047] At a reaction temperature of 300°C and a reaction mass space velocity of 0.8 h -1 , reaction pressure 0.1MPa, using the molecular sieve as S-1 catalyst, using C5 as raw material, the mass content of cis-pentadiene in the raw material is 61%, and the rest is C5 olefins, alkanes, etc. The reaction results are shown in Table 1.

[0048] Table 1

[0049]

[0050] [Example 2]

[0051] The silicon source is silica sol, the aluminum source is aluminum isopropoxide, the template agent is n-butylamine, the additive is diethanolamine, and the copolymer is PS-b-PMMA (molecular weight is 10000). 2 :0.4 n-Butylamine:500H 2 O Weigh solution A, Al 2 O 3 :0.2Diethanolamine:300H 2 O prepared solution B (Si / Al molar ratio of 50), slowly added the above solution B into solution A, and the formed molecular sieve gel precursor was introduced into an integrated ultra-gravity device for aging and crystallization, with a molar ratio of 0.2 copolymer: SiO 2 , add copolymer PS-b-PMMA, adjust the supergravity level to 100g, supergravity speed to 2000rpm, cycle 3 times, each cycle time is 20min, add pressure 0.3MPa, age for 72 hours, then pressurize 0.4MPa, crystallize at 150℃ for 24h, wash and dry after crystallization to obtain molecular sieve. The morphology of the molecular sieve is the same as Figure 1 In order to present the prismatic intercalation body morphology, the height h of the straight hexagonal prism in the prismatic intercalation body is 2-4 μm, the distance a between the two relatively larger sides of the straight hexagonal prism is 1-2 μm, and the length b of the bottom edge in the relatively larger side of the straight hexagonal prism is 1.5-3 times of a. The XRD diffraction pattern of the molecular sieve is the same as Figure 3 , which is ZSM-5 molecular sieve.

[0052] At a reaction temperature of 300°C and a reaction mass space velocity of 0.8 h -1 , reaction pressure 0.1MPa, using the molecular sieve as S-2 catalyst, using C5 as raw material, the mass content of cis-pentadiene in the raw material is 61%, and the rest is C5 olefins, alkanes, etc. The reaction results are shown in Table 2.

[0053] Table 2

[0054]

[0055] [Example 3]

[0056] The silicon source is silica sol, the aluminum source is aluminum isopropoxide, the template agent is n-butylamine, the additive is ammonium chloride, and the copolymer is PS-b-PMMA (molecular weight is 10000). 2 :0.3n-Butylamine:200H 2O Weigh solution A, Al 2 O 3 :10Ammonium chloride:200H 2 O prepared solution B (Si / Al molar ratio of 50), slowly added the above solution B into solution A, and the formed molecular sieve gel precursor was introduced into an integrated ultra-gravity device for aging and crystallization, with a molar ratio of 0.2 copolymer: SiO 2 , add copolymer PS-b-PMMA, adjust the supergravity level to 250g, supergravity speed to 2000rpm, cycle 3 times, each cycle time is 20min, add pressure 0.2MPa, age for 72 hours, then pressurize 0.4MPa, crystallize at 180℃ for 48h, wash and dry after crystallization to obtain molecular sieve. The morphology of the molecular sieve is the same as Figure 1 In order to present the prismatic intercalation body morphology, the height h of the straight hexagonal prism in the prismatic intercalation body is 2-4 μm, the distance a between the two relatively larger sides of the straight hexagonal prism is 1-2 μm, and the length b of the bottom edge in the relatively larger side of the straight hexagonal prism is 1.5-3 times of a. The XRD diffraction pattern of the molecular sieve is the same as Figure 3 , which is ZSM-5 molecular sieve.

[0057] At a reaction temperature of 300°C and a reaction mass space velocity of 0.8 h -1 , reaction pressure 0.1MPa, using the molecular sieve as S-3 catalyst, using C5 as raw material, the mass content of cis-pentadiene in the raw material is 61%, and the rest is C5 olefins, alkanes, etc. The reaction results are shown in Table 3.

[0058] Table 3

[0059]

[0060] [Example 4]

[0061] The silicon source is silica sol, the aluminum source is aluminum isopropoxide, the template agent is n-propylamine, the additive is diethanolamine, and the copolymer is P123. 2 :0.4n-propylamine:500H 2 O Weigh solution A, Al 2 O 3 :0.2Diethanolamine:300H 2 Solution B (Si / Al molar ratio of 50) was prepared by slowly adding the above solution B into solution A. The molecular sieve gel precursor formed was introduced into an integrated ultra-gravity device for aging and crystallization, with a molar ratio of 10P123:SiO 2, add copolymer P123, adjust the supergravity level to 150g, supergravity speed to 2000rpm, cycle 3 times, each cycle time is 20min, add pressure 0.3MPa, age for 72 hours, then pressurize 0.4MPa, crystallize at 150℃ for 24h, wash and dry after crystallization to obtain molecular sieve. The morphology of the molecular sieve is the same as Figure 1 In order to present the prismatic intercalation body morphology, the height h of the straight hexagonal prism in the prismatic intercalation body is 2-4 μm, the distance a between the two relatively larger sides of the straight hexagonal prism is 1-2 μm, and the length b of the bottom edge in the relatively larger side of the straight hexagonal prism is 1.5-3 times of a. The XRD diffraction pattern of the molecular sieve is the same as Figure 3 , which is ZSM-5 molecular sieve.

[0062] At a reaction temperature of 300°C and a reaction mass space velocity of 0.8 h -1 , reaction pressure 0.1MPa, using the molecular sieve as S-4 catalyst, C5 as raw material, the mass content of cis-pentadiene in the raw material is 61%, and the rest is C5 olefins, alkanes, etc. The reaction results are shown in Table 4.

[0063] Table 4

[0064]

[0065] [Example 5]

[0066] The silicon source is TEOS, the aluminum source is aluminum isopropoxide, the template agent is n-propylamine, the additive is diethanolamine, and the copolymer is P123. 2 :0.4n-propylamine:500H 2 O Weigh solution A, Al 2 O 3 :0.2Diethanolamine:300H 2 Solution B (Si / Al molar ratio of 50) was prepared by slowly adding the above solution B into solution A. The molecular sieve gel precursor formed was introduced into an integrated ultra-gravity device for aging and crystallization, with a molar ratio of 0.2P123:SiO 2 , add copolymer P123, adjust the supergravity level to 250g, supergravity speed to 2000rpm, cycle 3 times, each cycle time is 20min, add pressure 0.3MPa, age for 72 hours, then pressurize 0.4MPa, crystallize at 150℃ for 24h, wash and dry after crystallization to obtain molecular sieve. The morphology of the molecular sieve is the same as Figure 1In order to present the prismatic intercalation body morphology, the height h of the straight hexagonal prism in the prismatic intercalation body is 2-4 μm, the distance a between the two relatively larger sides of the straight hexagonal prism is 1-2 μm, and the length b of the bottom edge in the relatively larger side of the straight hexagonal prism is 1.5-3 times of a. The XRD diffraction pattern of the molecular sieve is the same as Figure 3 , which is ZSM-5 molecular sieve.

[0067] At a reaction temperature of 300°C and a reaction mass space velocity of 0.8 h -1 , reaction pressure 0.1MPa, using the molecular sieve as S-5 catalyst, C5 as raw material, the mass content of cis-pentadiene in the raw material is 61%, and the rest is C5 olefins, alkanes, etc. The reaction results are shown in Table 5.

[0068] Table 5

[0069]

[0070] [Comparative Example 1]

[0071] The silicon source is silica sol, the aluminum source is sodium aluminate, the template agent is n-propylamine, and the additive is diethanolamine. 2 :0.4n-propylamine:500H 2 O Weigh solution A, Al 2 O 3 :0.2Diethanolamine:300H 2 Solution B (Si / Al molar ratio of 50) was prepared, and the above solution B was slowly added to solution A. The formed molecular sieve gel precursor was passed into an integrated high gravity device for aging and crystallization without adding copolymer and pressure. The high gravity level was adjusted to 100g and the high gravity speed was 2000rpm. The cycle was repeated 3 times, each cycle lasting 20min. After aging for 72 hours, the product was crystallized at 150°C for 24h. After crystallization, the product was washed and dried to obtain a spherical molecular sieve. Figure 2 Obviously, the morphology is different from that of the molecular sieve of the present invention. The XRD diffraction pattern of the molecular sieve is the same as Figure 3 ,Depend on Figure 3 It can be known to be ZSM-5 molecular sieve.

[0072] At a reaction temperature of 300°C and a reaction mass space velocity of 0.8 h -1 , reaction pressure 0.1MPa, using this molecular sieve as D-1 catalyst, using C5 as raw material, the mass content of cis-pentadiene in the raw material is 61%, and the rest is C5 olefins, alkanes, etc. The reaction results are shown in Table 6.

[0073] Table 6

[0074]

[0075] [Comparative Example 2]

[0076] The silicon source is silica sol, the aluminum source is aluminum isopropoxide, the template agent is n-propylamine, and the additive is diethanolamine. 2 :0.4n-propylamine:500H 2 O Weigh solution A, Al 2 O 3 :0.2Diethanolamine:300H 2 O prepares solution B (Si / Al molar ratio is 50), slowly adds the above solution B into solution A, and the formed molecular sieve gel precursor is passed into an integrated high gravity device for aging and crystallization without adding copolymer, and the pressure is 0.3 MPa. The high gravity level is adjusted to 100 g, the high gravity speed is 2000 rpm, and the cycle is repeated 3 times, each cycle time is 20 min. After aging for 72 hours, the pressure is increased by 0.4 MPa again, and crystallization is carried out at 150°C for 24 hours. After crystallization, the spherical molecular sieve is obtained by washing and drying.

[0077] At a reaction temperature of 300°C and a reaction mass space velocity of 0.8 h -1 , reaction pressure 0.1MPa, using this molecular sieve as D-2 catalyst, using C5 as raw material, the mass content of cis-pentadiene in the raw material is 61%, and the rest is C5 olefins, alkanes, etc. The reaction results are shown in Table 7.

[0078] Table 7

[0079]

[0080] [Comparative Example 3]

[0081] The silicon source is silica sol, the aluminum source is aluminum isopropoxide, the template is n-propylamine, the additive is diethanolamine, and the copolymer is P123. 2 :0.4n-propylamine:500H 2 O Weigh solution A, Al 2 O 3 :0.2Diethanolamine:300H 2 Solution B (Si / Al molar ratio of 50) was prepared by slowly adding the above solution B into solution A. The molecular sieve gel precursor formed was introduced into an integrated ultra-gravity device for aging and crystallization, with a molar ratio of 0.2P123:SiO 2 , add copolymer P123, without adding pressure, adjust the supergravity level to 100g, the supergravity speed to 2000rpm, cycle 3 times, each cycle time is 20min, after aging for 72 hours, crystallize at 150℃ for 24h, and obtain spherical molecular sieve after washing and drying.

[0082] At a reaction temperature of 300°C and a reaction mass space velocity of 0.8 h -1, reaction pressure 0.1MPa, using this molecular sieve as D-3 catalyst, using C5 as raw material, the mass content of cis-pentadiene in the raw material is 61%, and the rest is C5 olefins, alkanes, etc. The reaction results are shown in Table 8.

[0083] Table 8

[0084]

[0085] The above embodiments describe the preferred embodiments of the present invention in detail, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for producing trans-pentadiene, comprising: Cis-pentadiene is used as a reaction raw material and reacts in the presence of a solid phase catalyst to produce trans-pentadiene; The solid phase catalyst is a ZSM-5 molecular sieve, and the molecular sieve is a prism intercalation body formed by two straight hexagonal prisms vertically crossing each other.

2. The production method according to claim 1, characterized in that The cis-pentadiene is C5 cis-piperylene. Preferably, the mass content of cis-pentadiene in the cis-pentadiene raw material is 10%-100%.

3. The production method according to claim 1, characterized in that The reaction conditions are: reaction temperature of 200°C-600°C, reaction pressure of 0-0.5MPa, liquid phase mass space velocity of 0.1-10h -1 .

4. The production method according to claim 1, characterized in that In the prismatic interpenetrating body, each of the two right hexagonal prisms has two relatively large sides and four relatively small sides, the two relatively large sides are parallel, and there are two relatively small sides between the two relatively large sides. In the prismatic interpenetrating body, the relatively large sides of the two right hexagonal prisms are perpendicular to and penetrate each other, and the two adjacent relatively small sides of the two right hexagonal prisms are in the same projection direction.

5. The production method according to claim 4, characterized in that: The height h of the right hexagonal prism is 2-4 μm; optionally, the distance a between the two relatively larger sides of the right hexagonal prism is 1-2 μm; optionally, the length b of the bottom edge of the relatively larger side of the right hexagonal prism is 1.5-3 times of a.

6. The production method according to claim 1, characterized in that: The atomic molar ratio of silicon to aluminum Si / Al of the ZSM-5 molecular sieve is 20-∞.

7. The production method according to claim 1, characterized in that: The preparation method of the ZSM-5 molecular sieve comprises the following steps: mixing a silicon source, an aluminum source, an additive, a template and water to obtain a molecular sieve gel precursor, then adding the precursor and the copolymer into an integrated high-gravity device for aging and crystallization, pressurizing and rotating under high gravity, cycling, aging after completion, and then crystallizing under secondary pressurization to obtain the ZSM-5 molecular sieve.

8. The production method according to claim 7, characterized in that: The copolymer includes at least one of a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer; the copolymer is preferably selected from at least one of P123, polystyrene-b-polymethyl methacrylate, and polybutadiene-styrene copolymer; preferably, the molar ratio of the copolymer to the silicon source in terms of SiO2 is 0.05-10, preferably 0.2-10.

9. The production method according to claim 7, characterized in that: The additive is at least one of urea, diethanolamine, ammonium chloride and ammonia water.

10. The production method according to claim 7, characterized in that: The pressurization pressure is 0.01-10MPa, preferably 0.05-8MPa; and / or, the increased pressure of the secondary pressurization is 0.01-10MPa, preferably 0.1-8MPa; and / or, the crystallization conditions are a crystallization temperature of 100-200°C and a crystallization time of 1-96h.

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