阅读说明：本技术 一种异构烷烃溶剂及其制备方法 (Isoparaffin solvent and preparation method thereof ) 是由 杨海兰 钟东文 廖定满 卢振旭 谭思 李洁 郑镇昭 孙望平 谢正良 于 2019-10-30 设计创作，主要内容包括：本发明公开了一种异构烷烃溶剂及其制备方法,该方法包括：将异壬醇副产物在催化剂存在下与氢气进行加氢反应,得到异构烷烃；将所述异构烷烃进行精馏,得到相应的异构烷烃溶剂,所述异壬醇副产物含有C8烯烃、C12烯烃和C16烯烃中的一种或多种。根据本发明,能够得到良好品质的相应异构烷烃溶剂,为获得异构烷烃提供了一条崭新路线,填补了本领域利用异壬醇装置副产物制备异构烷烃溶剂的空白。(The invention discloses an isoparaffin solvent and a preparation method thereof, wherein the method comprises the following steps: carrying out hydrogenation reaction on the isononyl alcohol by-product and hydrogen in the presence of a catalyst to obtain isoparaffin; and (3) rectifying the isoparaffin to obtain a corresponding isoparaffin solvent, wherein the isononanol by-product contains one or more of C8 olefin, C12 olefin and C16 olefin. According to the invention, the corresponding isoparaffin solvent with good quality can be obtained, a brand-new route is provided for obtaining isoparaffin, and the blank that the isoparaffin solvent is prepared by using the byproduct of the isononanol device in the field is filled.)

1. A method for preparing an isoparaffin solvent, comprising:

carrying out hydrogenation reaction on the isononyl alcohol by-product and hydrogen in the presence of a catalyst to generate isoparaffin;

rectifying the isoparaffin to obtain a corresponding isoparaffin solvent;

wherein the isononanol by-product comprises one or more of a C8 olefin, a C12 olefin and a C16 olefin.

2. The process of claim 1, wherein the conditions of the hydrogenation reaction comprise: the volume ratio of the hydrogen to the isononyl alcohol by-product is 200-500: 1.

3. The process of claim 1 or 2, wherein the hydrogenation conditions further comprise: the volume space velocity of the isononyl alcohol by-product is 0.5-3.5 h^-1。

4. The process of any one of claims 1-3, wherein the hydrogenation conditions further comprise: the hydrogen partial pressure in the reactor is kept at 0.5-10 MPa, and the reaction temperature is 130-280 ℃.

5. The method of claim 1, wherein the catalyst is a platinum and/or palladium metal catalyst.

6. The method according to claim 1 or 5, wherein the catalyst is prepared by taking platinum and/or palladium as an active metal component and taking alumina as a carrier, and the catalyst is FMTA-2.

7. The method of claim 1, wherein the hydrogenation reaction conditions of the C8 olefin in the isononanol by-product comprise: the hydrogen partial pressure is 3.0MPa, and the volume space velocity is 1.0h^-1The reaction temperature is 220 ℃, and the volume ratio of hydrogen to C8 olefin is 400: 1.

8. the method of claim 1, wherein the hydrogenation reaction conditions of the C12 olefin in the isononanol by-product comprise: the hydrogen partial pressure is 3.0MPa, and the volume space velocity is 1.2h^-1The reaction temperature is 220 ℃, and the volume ratio of hydrogen to C8 olefin is 400: 1.

9. the method of claim 1, wherein the hydrogenation reaction conditions of the C16 olefin in the isononanol by-product comprise: the hydrogen partial pressure is 1.5-3.0 MPa, and the volume space velocity is 1.0h^-1The reaction temperature is 200-220 ℃, and the volume ratio of hydrogen to C8 olefin is 400: 1.

10. an isoparaffin solvent produced by the method for producing an isoparaffin solvent according to any one of claims 1 to 9.

Technical Field

The invention relates to preparation of an isoparaffin solvent, in particular to an isoparaffin solvent and a method for preparing the isoparaffin solvent by using a byproduct of an isononanol device.

Background

Petroleum hydrocarbon solvents generally comprise four classes of compounds: normal paraffins, isoparaffins, naphthenes and aromatics. The influence of the four compounds on the properties of the solvent oil is respectively characterized. The properties of hydrocarbon solvents are mainly odor, toxicity, solubility, low temperature performance and suitable distillation range. Aromatic hydrocarbon is a main source of smell and toxicity, is a compound which is removed as far as possible from the petroleum hydrocarbon solvent, and naphthenic hydrocarbon has better solubility and low-temperature performance but larger smell among the other three compounds, and is a main source of smell of the petroleum hydrocarbon solvent except the aromatic hydrocarbon; n-alkanes have little odor, but poor solubility and low temperature performance; the isoparaffin has the solubility similar to that of cycloparaffin, good low-temperature performance and little odor, and is the hydrocarbon solvent with the best comprehensive performance. The isoparaffin solvent can be widely applied to the application fields of paint, printing ink, coating, cosmetics, metal processing, peroxide dispersant and the like.

Foreign isoparaffin solvent production enterprises mainly comprise an Exxon petroleum company, a Japan bright-dipping petroleum company and the like, and the isoparaffin is prepared by adopting a process of isomerizing carbon tetramerization-hydrofining. The production process produces a series of products such as isomeric octane, isomeric dodecane, isomeric hexadecane, isomeric eicosane and the like, and the table 1 shows the properties of typical isomeric alkane solvent oil of foreign companies.

TABLE 1 quality index of isoparaffin solvent from foreign company

The yield of domestic hydrocarbon solvents exceeds 200 million tons/year, the hydrocarbon solvents are mainly produced by oil refining enterprises, the production characteristics are that the varieties are single, the majority of commodities are used as main products, wherein plant extraction solvents, rubber solvents and paint solvents account for most of the proportion, the special products are few, no enterprises produce isoparaffin solvents at present at home, and the used isoparaffins are imported products.

In addition, the famous petrochemical and foreign capital co-constructed isononyl alcohol production device has been built into operation in 2016, and 3.3 ten thousand tons/year of isododecene and 1 ten thousand tons/year of isohexadecene by-products are produced after the device is put into operation. Therefore, the invention is urgently needed to develop a preparation method for preparing an isoparaffin solvent by utilizing the byproducts of the isononanol device.

At present, no enterprises and related technologies for producing isoparaffin solvents exist in China. The method for preparing the isoparaffin solvent by utilizing the isononanol device byproduct can fill the blank in the field.

Disclosure of Invention

In view of the huge market prospect of isoparaffin and the limitations of the existing preparation method, the invention provides an isoparaffin solvent and a preparation method thereof, in particular to a method for preparing the isoparaffin solvent by utilizing the byproduct of an isononanol device.

In order to solve the above technical problems, the present invention provides a method for preparing an isoparaffin solvent, comprising:

carrying out hydrogenation reaction on the isononyl alcohol by-product and hydrogen in the presence of a catalyst to generate isoparaffin;

rectifying the isoparaffin to obtain corresponding isoparaffin solvent,

wherein the isononanol by-product comprises one or more of a C8 olefin, a C12 olefin and a C16 olefin.

The method provided by the invention is suitable for isononyl alcohol byproducts containing C8 olefin, C12 olefin and C16 olefin which are mixed according to various proportions. According to embodiments of the invention, the isononanol by-product may include C8 olefin 0.8t/a, C12 olefin 3.3t/a and C16 olefin 1.0t/a in annual yield.

In the present invention, the C8 olefin, C12 olefin and C16 olefin all refer to corresponding isoolefins.

In the invention, the rectification is precision cutting fractionation which is a commonly used rectification mode in the field, and the distillation range of the cutting is controlled within a small range due to the narrow distillation range, so the distillation range is called as precision cutting, and the rectification process can be obtained according to the conventional test.

According to an embodiment of the present invention, the hydrogenation reaction is performed in a reactor, which may be a reactor cast from stainless steel, such as a fixed bed reactor, within the pressure and temperature ranges capable of withstanding the hydrogenation reaction tests.

In an embodiment of the present invention, the conditions of the hydrogenation reaction include: the volume ratio of the hydrogen to the isononyl alcohol by-product is 200-700: 1. Preferably, the volume ratio of the hydrogen to the isononyl alcohol by-product is 200-500: 1. More preferably, the volume ratio of the hydrogen to the isononyl alcohol by-product is 300-500: 1.

In an embodiment of the present invention, the conditions of the hydrogenation reaction further comprise: the volume space velocity of the isononyl alcohol by-product is 0.5-3.5 h^-1(ii) a Further preferably, the volume space velocity of the isononyl alcohol by-product is 1.0-2.0 h^-1。

In an embodiment of the present invention, the conditions of the hydrogenation reaction may further include: the hydrogen partial pressure in the reactor is kept at 0.5-10 MPa, and the reaction temperature is 130-280 ℃. Preferably, the conditions of the hydrogenation reaction may further include: the hydrogen partial pressure in the reactor is kept at 1.5-3 MPa, and the reaction temperature is 170-220 ℃.

In an embodiment of the invention, the catalyst is a platinum and/or palladium metal catalyst. In the embodiment of the invention, the catalyst is prepared by taking platinum and/or palladium as an active metal component and taking alumina as a carrier, and the catalyst is FMTA-2 developed by FRIPP. In the present invention, the amount of the catalyst is determined according to the volume of the reactor, and space velocity is mainly ensured.

In an embodiment of the present invention, the hydrogenation reaction conditions of the C8 olefin in the isononanol by-product include: the hydrogen partial pressure is 3.0MPa, and the volume space velocity is 1.0h^-1The reaction temperature is 220 ℃, and the volume ratio of hydrogen to C8 olefin is 400: 1.

in an embodiment of the present invention, the hydrogenation reaction conditions using the C12 olefin in the isononanol by-product as a raw material include: the hydrogen partial pressure is 3.0MPa, and the volume space velocity is 1.2h^-1The reaction temperature is 220 ℃, and the volume ratio of hydrogen to C8 olefin is 400: 1.

in an embodiment of the present invention, the hydrogenation reaction conditions using the C16 olefin in the isononanol by-product as a raw material include: the hydrogen partial pressure is 1.5-3.0 MPa, and the volume space velocity is 1.0h^-1The reaction temperature is 200-220 ℃, and the volume ratio of hydrogen to C8 olefin is 400: 1.

the invention also provides an isoparaffin solvent prepared by the preparation method of the isoparaffin solvent, and the isoparaffin solvent can meet the requirements of various quality indexes of the corresponding solvent.

According to the preparation method of the isoparaffin solvent, provided by the invention, iso-nonanol byproduct raw materials such as C8 olefin, C12 olefin and C16 olefin are respectively subjected to hydrofining to saturate iso-olefins, and the obtained iso-paraffins are subjected to precise fractionation to obtain products such as iso-octane (C8), C12 iso-paraffins, C16 iso-paraffins and C20 iso-paraffins which meet the index requirements. Provides a new way for obtaining isoparaffin, fills the gap of preparing isoparaffin solvent by using the byproduct of the isononyl alcohol device in the field, and has wide prospect.

Drawings

The invention will be described below with reference to the accompanying drawings.

Fig. 1 is a process flow diagram of a preparation method of an isoparaffin solvent according to an embodiment of the present invention.

Detailed Description

In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

In the present invention, the raw materials or components used may be commercially or conventionally prepared unless otherwise specified.

The catalyst was FMTA-2 developed by FRIPP.

Example 1C 8 olefin hydrogenation Process run

This example illustrates the case of starting with the C8 olefin in the isononanol by-product.

A process for preparing the solvent of isoalkane includes such steps as feeding the by-product C8 isononanol (isomeric C8 olefin) to reactor (fixed-bed reactor) at a certain space velocity, introducing hydrogen in the presence of catalyst (200ml FMTA-2) for hydrogenation reaction, and rectifying the obtained isoalkane to obtain the solvent of isoalkane. Wherein the process conditions were controlled as shown in Table 2.

TABLE 2C 8 Process conditions for hydrofinishing olefins

TABLE 3C 8 Isoalkane product Properties under different conditions

As can be seen from the data in Table 3, the acidity of the resulting oil and the bromine index were both 0 at each reaction condition. Especially when the hydrogen partial pressure/Mpa is 3.0, the volume space velocity h^-1The reaction temperature is 220 ℃, and the volume ratio of hydrogen to oil is 400, and the infrared qualitative characterization result shows that the oxide in the isononanol by-product C8 olefin is completely removed. By rectification (precision cut fractionation) and steamThe extracted distillate with the temperature of more than 73 ℃ can completely produce C8 isoparaffin products meeting the index requirements, and the specific measurement indexes are shown in Table 4.

TABLE 4C 8 isoparaffin solvent Properties

Item	Product Properties	Outbound IP 1016	Analytical method
				Fraction Range/. degree.C	>73	73～140	GB/T 6536
Flash point (closed)/°c	22	-12	GB/T 261
				Content of isoparaffin,% of	98.59	≮98	SH/T 0741
Aromatic content/. mu. g.g-1	0.56	≯1	SH/T 0409
				Sulfur/. mu. g.g-1	<1.0	≯1	SH/T0253-1992
Bromine number/mgBr.100g-1	0	≯10	SH/T 0630
				Color (Saybolt)/number	>+30		GB/T 3555

Example 2C 12 olefin hydrogenation Process run

This example illustrates the case of starting with the C12 olefin in the isononanol by-product.

A process for preparing the solvent of isoalkane includes such steps as feeding the by-product C12 isononanol olefin (isomeric C12 olefin) to reactor (fixed-bed reactor) at a certain space velocity, introducing hydrogen in the presence of catalyst (200ml FMTA-2) for hydrogenation reaction, and rectifying the isoalkane to obtain the solvent of isoalkane. Wherein, the process conditions and the investigation results are shown in Table 5.

TABLE 5C 12 hydrogenation Process Condition review

As can be seen from the data in Table 5, C12 olefin is used as the raw material, and the hydrogen partial pressure is 1.5-3.0 MPa, the reaction temperature is 220 ℃, and the space velocity is 1.0-1.5 h^-1And under the process condition that the hydrogen-oil ratio is 400:1, the bromine index and the acidity of the oil generated by hydrogenation are both 0, and the content of isoparaffin is more than 98%. Especially when the hydrogen partial pressure/Mpa is 3.0, the volume space velocity/h^-1The distillation range of C12 olefin raw material and produced oil is heavier under the conditions that the reaction temperature is 220 ℃ and the volume ratio of hydrogen to oil is 400, the initial boiling point of the raw material is 191 ℃, the 5 percent point of the distillation range of the produced oil is higher than 192 ℃, the dry point is about 211 ℃, the requirements of C12 isoparaffin solvent (light extraction IP 1620) with the distillation range of 166-202 ℃ can be met, and the specific measurement indexes are shown in Table 6.

TABLE 6C 12 isoparaffin solvent Properties

Example 3C 16 olefin hydrogenation Process run

This example illustrates the case of starting with the C16 olefin in the isononanol by-product.

A method for preparing isoparaffin solvent comprises the steps of feeding isononyl alcohol by-product C16 olefin (isomeric C16 olefin) into a reactor (fixed bed reactor) according to a certain space velocity, introducing hydrogen for hydrogenation reaction in the presence of a catalyst (200ml FMTA-2), and after the reaction is finished, precisely cutting and fractionating the obtained isoparaffin to obtain corresponding isoparaffin solvent product, wherein the process conditions comprise: hydrogen partial pressure of 3.0MPa, volume space velocity of 1.0h^-1The reaction temperature is 220 ℃, and the volume ratio of hydrogen to oil is 400. The product properties are shown in tables 7, 8 and 9, respectively.

TABLE 7210-270 ℃ fraction properties

The data in Table 7 show that the C16 isoparaffin content of the fraction obtained under the process condition at the temperature of 210-270 ℃ is 99.4 percent, the bromine index is 0, the aromatic hydrocarbon content is 0.49 mu g/g, the closed-mouth flash point is 103 ℃, and the sulfur content is less than 1.0 mu g.g^-1And meets the quality index requirement of the luminous IP 2028 isoparaffin solvent.

TABLE 8 >270 ℃ distillate Properties

Item	Product Properties	Light-emitting IP 2835	Analytical method
				Fraction Range/. degree.C	>275	275～335	GB/T 6536
Density/kg.m-3	829.8	820	GB/T 1884-1885
				Content of C16 isoparaffin%	98.36	≮98	SH/T 0741
Content of isoparaffin,% of	98.6	≮98	SH/T 0741
				Content of C12 isoparaffin%	0.24	Not more than 2	SH/T 0741
Initial boiling point/. degree.C	275	275	GB/T 6536
				End point/. degree.C	334	335	GB/T 6536
Aromatic content/. mu. g.g-1	0.68	Not more than 1	SH/T 0409
				Sulfur/. mu. g.g-1	<1.0	Not more than 2	SH/T 0689
Nitrogen/. mu. g.g-1	<1.0	Not more than 1	SH/T 0657
				Bromine index/gBr. (100g)-1	0	Not more than 100	SH/T 0630
Color (Saybolt)/number			GB/T 3555

The data in Table 8 show that the aromatic hydrocarbon content of the distillate obtained under the process condition at the temperature of 270 ℃ is 0.68 mu g/g, the content of C20 isoparaffin is 98.6 percent, the bromine index is 0, the content of sulfur and nitrogen is less than 1.0 mu g/g, and the obtained product can be used as a C20 isoparaffin solvent meeting the quality requirement of light extraction IP 2835.

TABLE 9 <210 ℃ distillate Properties

As can be seen from the data in Table 9, the fraction aromatic hydrocarbon content at the temperature of <210 ℃ obtained under the process conditions is 0.5 mu g/g, the C12 isoparaffin content is 98.12 percent, the bromine index is 0, and the sulfur and nitrogen contents are both less than 1.0 mu g/g, so that the solvent can be used as a C12 isoparaffin solvent meeting the quality requirement of light IP 1620.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.