Crystallization purification method of indene in C9 petroleum resin and application

Abstract

The invention discloses a crystallization purification method of indene in C9 petroleum resin, which comprises the following steps: S1, pretreating the C9 petroleum resin to obtain concentrated indene; s2, mixing the concentrated indene with a solvent I, performing primary cooling crystallization, and filtering after heat preservation to obtain crystals and filtrate; s3, mixing the crystals with a solvent II, carrying out secondary cooling crystallization, carrying out heat preservation, and filtering to obtain a filter cake; and S4, dissolving the filter cake, and carrying out negative pressure distillation to remove the solvent so as to obtain indene. According to the method, low-temperature crystallization is adopted, target substances can be selectively separated out, impurities are effectively removed, and a C9 petroleum resin mixture with large solubility difference is separated. And moreover, the crystals cannot be caked or caked during precipitation, the dispersion difficulty is low, filtration is easy, and the process difficulty is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of carbocyclic compounds, in particular to a crystallization purification method of indene in carbon nine petroleum resin and application thereof. BACKGROUND

[0002] Indene mainly exists in coal tar and petroleum distillate, indene is insoluble in water, can be mixed with ethanol or diethyl ether, has high chemical activity of olefin bond, and is easy to polymerize or add. Indene has a wide range of applications, and plays an important role in the fields of pesticides, resins, medicines and the like. However, the purity of indene in cracked petroleum is not high, and it is difficult to purify, usually used together with gasoline as a solvent, resulting in a large amount of data waste, so it is very important to develop a simple purification process and a process which is easy to use after purification.

[0003] Chinese patent application CN105967971A discloses a freezing crystallization purification method of indene in cracked carbon nine, directly freezing and crystallizing the concentrated indene solution, and then gradually increasing the freezing crystallization temperature of the crystal, thereby obtaining high-purity indene, but no solvent is added in the experiment, and the crystal is difficult to disperse after precipitation, and difficult to filter. Chinese patent application CN105837394B discloses a purification method of high-purity 1,3,5-trimethylbenzene, which uses a rectifying column to perform vacuum gradient rectification on the system, reduces the boiling point of the mixture in the mixed C9 aromatic hydrocarbon solvent oil raw material liquid, increases the relative volatility between components, reduces the separation difficulty, and improves the product yield, but high-purity separation of indene cannot be achieved. SUMMARY

[0004] In order to develop a simple purification process and a process which is easy to use after purification of indene, the first aspect of the present application provides a crystallization purification method of indene in carbon nine petroleum resin, comprising the following steps:

[0005] S1: pretreating carbon nine petroleum resin to obtain concentrated indene;

[0006] S2: mixing the concentrated indene with a solvent I, once cooling and crystallizing, filtering after insulation to obtain crystals and filtrate;

[0007] S3: mixing the crystals with a solvent II, twice cooling and crystallizing, filtering after insulation to obtain a filter cake;

[0008] S4: dissolving the filter cake, removing the solvent by negative pressure distillation to obtain indene.

[0009] As an implementation manner, the temperature of the once cooling and crystallizing is-40℃ to-20℃.

[0010] As an implementation manner, the temperature of the once cooling and crystallizing is-30℃ to-20℃.

[0011] As an implementation form, the temperature of the secondary cooling crystallization is -40℃ to -10℃.

[0012] As an implementation form, the temperature of the secondary cooling crystallization is -30℃ to -10℃.

[0013] As an implementation form, the pre-treatment process of the carbon nine petroleum resin is negative pressure distillation, the temperature of the negative pressure distillation is 100℃ to 200℃, and the pressure of the negative pressure distillation is -0.01MPa to -0.095MPa.

[0014] As an implementation form, the pre-treatment process of the carbon nine petroleum resin is negative pressure distillation, the temperature of the negative pressure distillation is 90℃ to 150℃, and the pressure of the negative pressure distillation is -0.01MPa to -0.095MPa.

[0015] As an implementation form, the carbon nine petroleum resin includes methylstyrene, C 10 H 14 Polycyclic olefins, indene, 1-methyl-3-propylbenzene, 1,2-dimethyl-4-ethylbenzene, 1-methyl-4-propylbenzene.

[0016] As an implementation form, the mass ratio of the concentrated indene to the solvent one is (1-3):(1-3).

[0017] As an implementation form, the mass ratio of the concentrated indene to the solvent one is 1:1.

[0018] As an implementation form, the mass ratio of the crystal to the solvent two is (1-3):(1-3).

[0019] As an implementation form, the mass ratio of the crystal to the solvent two is 1:1.

[0020] As an implementation form, the solvent one and the solvent two both include at least one of toluene, ethanol, and isopropanol.

[0021] As an implementation form, the temperature of the negative pressure distillation in S4 is 60℃ to 200℃, and the pressure of the negative pressure distillation is -0.01MPa to -0.095MPa.

[0022] As an implementation form, the temperature of the negative pressure distillation in S4 is 60℃ to 100℃, and the pressure of the negative pressure distillation is -0.03MPa to -0.09MPa.

[0023] As an implementation form, the temperature of the negative pressure distillation in S4 is 100℃, and the pressure of the negative pressure distillation is -0.06MPa.

[0024] As an implementation form, the holding time of S2 and S3 is 0 to 4h.

[0025] As an implementation form, the holding time of S2 and S3 is 1-3h.

[0026] As an implementation form, the holding time of S2 and S3 is 2h.

[0027] The second aspect of the application provides an application of the crystallization purification method of indene in carbon nine petroleum resin, which is applied to the preparation of high-purity indene with a purity of ≥97%.

[0028] Compared with the prior art, the application has the following beneficial effects:

[0029] (1) The crystallization purification method of indene in carbon nine petroleum resin can selectively precipitate target substances, effectively remove impurities, and separate C9 petroleum resin mixtures with large solubility differences by low-temperature crystallization.

[0030] (2) The crystallization purification method of indene in carbon nine petroleum resin mixes concentrated indene with a solvent, and then performs low-temperature crystallization. The crystals do not form agglomerates or clumps when precipitated, have low dispersion difficulty, are easy to filter, and reduce the process difficulty.

[0031] (3) The crystallization purification method of indene in carbon nine petroleum resin adopts a volume ratio of 1:1 for concentrated indene or crystals and a solvent, and is matched with low-temperature crystallization, so that the reaction conditions are more moderate, and the decomposition of indene at high temperature is avoided.

[0032] (4) The crystallization purification method of indene in carbon nine petroleum resin adopts twice low-temperature crystallization at different temperatures, which can improve the purity of indene and obtain high-purity indene, which is convenient for subsequent application.

[0033] (5) The crystallization purification method of indene in carbon nine petroleum resin can control the size, shape and crystal form of the crystals by changing the conditions such as solvent, temperature and concentration, and improve the performance of the product. DETAILED DESCRIPTION

[0034] Example 1

[0035] A crystallization purification method of indene in carbon nine petroleum resin comprises the following steps:

[0036] S1: pretreating carbon nine petroleum resin to obtain concentrated indene;

[0037] S2: mixing 1000g of concentrated indene with a solvent, once cooling and crystallization, filtering after holding, to obtain crystals and filtrate;

[0038] S3: mixing the crystals with a second solvent, twice cooling and crystallization, filtering after holding, to obtain a filter cake;

[0039] S4: dissolving the filter cake, removing the solvent by negative pressure distillation to obtain indene.

[0040] The pre-treatment of the carbon nine petroleum resin is negative pressure distillation, the temperature of the negative pressure distillation is 120℃, and the pressure of the negative pressure distillation is -0.095MPa.

[0041] The mass ratio of the concentrated indene to the solvent one is 1:1;

[0042] The mass ratio of the crystal to the solvent two is 1:1;

[0043] The solvent one and the solvent two are both toluene;

[0044] The temperature of the first cooling crystallization is -35℃, and the temperature of the second cooling crystallization is -25℃.

[0045] The temperature of the negative pressure distillation in S4 is 100℃, and the pressure of the negative pressure distillation is -0.06MPa.

[0046] The holding time of S2 and S3 is both 2h.

[0047] Embodiment 2

[0048] A crystallization purification method of indene in a carbon nine petroleum resin, comprising the following steps:

[0049] S1: pre-treating the carbon nine petroleum resin to obtain concentrated indene;

[0050] S2: mixing 1000g of the concentrated indene with a solvent one, first cooling crystallization, holding, and then filtering to obtain crystals and a filtrate;

[0051] S3: mixing the crystals with a solvent two, second cooling crystallization, holding, and then filtering to obtain a filter cake;

[0052] S4: dissolving the filter cake, removing the solvent by negative pressure distillation to obtain indene.

[0053] The pre-treatment of the carbon nine petroleum resin is negative pressure distillation, the temperature of the negative pressure distillation is 120℃, and the pressure of the negative pressure distillation is -0.095MPa.

[0054] The mass ratio of the concentrated indene to the solvent one is 1:1;

[0055] The mass ratio of the crystal to the solvent two is 1:1;

[0056] The solvent one and the solvent two are both ethanol;

[0057] The temperature of the first cooling crystallization is -24℃, and the temperature of the second cooling crystallization is -20℃.

[0058] The temperature of the negative pressure distillation in S4 is 100 DEG C, and the pressure of the negative pressure distillation is -0.06 MPa.

[0059] The holding time of S2 and S3 is 2 h.

[0060] Example 3

[0061] A crystallization purification method of indene in carbon nine petroleum resin, comprising the following steps:

[0062] S1: pretreating carbon nine petroleum resin to obtain concentrated indene;

[0063] S2: mixing 1000 g of the concentrated indene with solvent one, once cooling crystallization, holding after filtration to obtain crystals and filtrate;

[0064] S3: mixing the crystals with solvent two, twice cooling crystallization, holding after filtration to obtain filter cake;

[0065] S4: dissolving the filter cake, removing the solvent by negative pressure distillation to obtain indene.

[0066] The pretreatment of the carbon nine petroleum resin is negative pressure distillation, the temperature of the negative pressure distillation is 120 DEG C, and the pressure of the negative pressure distillation is -0.095 MPa.

[0067] The mass ratio of the concentrated indene and solvent one is 1:1;

[0068] The mass ratio of the crystals and solvent two is 1:1;

[0069] The solvent one and solvent two are both isopropyl alcohol;

[0070] The temperature of the once cooling crystallization is -37 DEG C, and the temperature of the twice cooling crystallization is -15 DEG C.

[0071] The temperature of the negative pressure distillation in S4 is 100 DEG C, and the pressure of the negative pressure distillation is -0.06 MPa.

[0072] The holding time of S2 and S3 is 2 h.

[0073] Example 4

[0074] A crystallization purification method of indene in carbon nine petroleum resin, comprising the following steps:

[0075] S1: pretreating carbon nine petroleum resin to obtain concentrated indene;

[0076] S2: mixing 1000 g of the concentrated indene with solvent one, once cooling crystallization, holding after filtration to obtain crystals and filtrate;

[0077] S3: mixing the crystals with solvent two, twice cooling crystallization, holding after filtration to obtain filter cake;

[0078] S4: dissolving the filter cake, removing the solvent by negative pressure distillation to obtain indene.

[0079] The pre-treatment of the carbon nine petroleum resin is negative pressure distillation, the temperature of the negative pressure distillation is 120℃, and the pressure of the negative pressure distillation is -0.095MPa.

[0080] The mass ratio of the concentrated indene to the solvent one is 1:1.2;

[0081] The mass ratio of the crystal to the solvent two is 1:1.2;

[0082] The solvent one and the solvent two are both ethanol;

[0083] The temperature of the first cooling crystallization is -25℃, and the temperature of the second cooling crystallization is -10℃.

[0084] The temperature of the negative pressure distillation in S4 is 100℃, and the pressure of the negative pressure distillation is -0.06MPa.

[0085] The holding time of S2 and S3 is both 2h.

[0086] Example 5

[0087] A crystallization purification method of indene in carbon nine petroleum resin, the specific implementation manner is same as that in example 2, and the difference is that the mass ratio of the concentrated indene to the solvent one is 1:0.8;

[0088] The mass ratio of the crystal to the solvent two is 1:0.8;

[0089] The temperature of the first cooling crystallization is -18℃.

[0090] Example 6

[0091] A crystallization purification method of indene in carbon nine petroleum resin, the specific implementation manner is same as that in example 2, and the difference is that the mass ratio of the concentrated indene to the solvent one is 1:0.6;

[0092] The mass ratio of the crystal to the solvent two is 1:0.6;

[0093] The temperature of the first cooling crystallization is -16℃.

[0094] Example 7

[0095] A crystallization purification method of indene in carbon nine petroleum resin, the specific implementation manner is same as that in example 2, and the difference is that the mass ratio of the concentrated indene to the solvent one is 1:0.4;

[0096] The mass ratio of the crystal to the solvent two is 1:0.4;

[0097] The temperature of the first temperature-lowering crystallization is -14℃.

[0098] Example 8

[0099] A crystallization and purification method of indene in carbon nine petroleum resin, the specific implementation manner is same as that of example 2, and the difference is that the mass ratio of the concentrated indene and the solvent one is 1:0.2;

[0100] The mass ratio of the crystal and the solvent two is 1:0.2;

[0101] The temperature of the first temperature-lowering crystallization is -12℃.

[0102] Performance test

[0103] 1. The yield of the first temperature-lowering crystallization product: yield=(the mass of the first temperature-lowering crystallization product / the mass of the concentrated indene)×100%

[0104] 3. The purity of indene: the initial temperature is 80℃, the holding time is 10min, the gradient temperature is raised, the first stage is raised to 200℃ at a rate of 5℃ / min, and the holding time is 30min; the second stage is raised to 300℃ at a rate of 20℃ / min, and the holding time is 10min, and the purity of indene is detected.

[0105] The test results are shown in table 1.

[0106] Table 1

[0107]

Claims

1. A method for crystallizing and purifying indene in C9 petroleum resin, characterized in that, Includes the following steps: S1: Pretreatment of C9 petroleum resin to obtain concentrated indene; S2: Mix concentrated indene with solvent one, cool and crystallize once, keep warm and then filter to obtain crystals and filtrate; S3: Mix the crystals with solvent II, cool and crystallize again, keep warm and then filter to obtain filter cake; S4: Dissolve the filter cake, remove the solvent by negative pressure distillation, and obtain indene.

2. The method for crystallizing and purifying indene in C9 petroleum resin according to claim 1, characterized in that, The temperature for the first cooling crystallization is -40℃ to -20℃.

3. The method for crystallizing and purifying indene in C9 petroleum resin according to claim 1, characterized in that, The temperature for the secondary cooling crystallization is -40℃ to -10℃.

4. The method for crystallizing and purifying indene in C9 petroleum resin according to claim 1, characterized in that, The pretreatment process for the C9 petroleum resin is negative pressure distillation, with a temperature of 100℃-200℃ and a pressure of -0.01MPa to -0.095MPa.

5. The method for crystallizing and purifying indene in C9 petroleum resin according to claim 2, characterized in that, The mass ratio of the concentrated indene to solvent one is (1-3):(1-3).

6. The method for crystallizing and purifying indene in C9 petroleum resin according to claim 3, characterized in that, The mass ratio of the crystal to solvent II is (1-3):(1-3).

7. The method for crystallizing and purifying indene in C9 petroleum resin according to claim 2, characterized in that, Solvent 1 and Solvent 2 each include at least one of toluene, ethanol, and isopropanol.

8. The method for crystallizing and purifying indene in C9 petroleum resin according to claim 1, characterized in that, The temperature of the negative pressure distillation in S4 is 60℃-200℃, and the pressure of the negative pressure distillation is -0.01MPa to -0.095MPa.

9. The method for crystallizing and purifying indene in C9 petroleum resin according to claim 1, characterized in that, The heat preservation time for both S2 and S3 is 0-4 hours.

10. An application of the crystallization and purification method for indene in C9 petroleum resin according to any one of claims 1-9, characterized in that, It is used in the preparation of high-purity indene, wherein the purity of the high-purity indene is ≥97%.

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