RU2252232C1 - Polypropylene composite as emulsion separator - Google Patents

Abstract

FIELD: polymer materials, in particular polypropylene composite useful in oil production, oil reprocessing, chemical industry, etc.

SUBSTANCE: claimed material consists polypropylene with melt flow index of 3-6 g/10 min; consists polypropylene with melt flow index of 13-25 g/10 min; fine dispersed filler (e.g., marble flour); stabilizing additive and zinc stearate and petrolatum oil as processing additives. Stabilizing additive represents pentaerythrite ester of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid. Material of present invention is useful in die casting production of various articles for separation of oil-and-water or petroleum-in-water dispersed systems.

EFFECT: material of improved strength, thermal resistance and chemical stability, as well as high melt flow index.

2 tbl, 5 ex

Description

The invention relates to the field of polymeric materials, namely to polypropylene-based composite materials, is intended for the manufacture by injection molding of coalescing baffles or plates of a coalescing emulsion separator bag, and can be used in the oil, oil refining, chemical and other industries where separation is required oil-water or oil-water disperse systems.

Currently, the oil industry is experiencing an increasing deterioration in the structure of oil reserves. As a part of the raw material base, the number of producing wells with high water cuts is increasing, so the separation of water from crude oil is one of the primary tasks of the oil industry. There is also the problem of separating oil-water emulsions, for example, transformer oil and water. To solve these problems in world practice using various methods and devices, including using a variety of polymeric materials.

A number of apparatuses are known for separating oil-water or oil-water emulsions, the main unit of which is a coalescing partition (a.s. SU No. 1837929, IPC B 01 D 17/028, publ. 30,08.1993, B.I. No. 32; the partition is made of hydrophobic carbon-containing material) or a coalescing package in the form of a set of inclined shelves mounted with the formation of wavy planes (a.s. SU No. 1733038, IPC B 01 D 17/02, publ. 05/15/1992, B.I. No. 18; shelves are made from a PTFE film) or in the form of a package of parallel plates that have protrusions, I raise running along one side and descending along the other side of the plates in the direction of movement of the emulsion (patent SU No. 2038113, IPC B 01 D 17/02, publ. 06/27/1995, BI No. 18; plates are made of hydrophobic structural material) or another design aimed at organizing the movement of coagulated particles of light (oil or oil) and heavy (water) phases to ensure their separate movement.

It should be noted that a prerequisite for the operability of materials used for the manufacture of coalescing baffles or plates of a coalescing emulsion separator package is hydrophobicity, since the process of particle enlargement is due to contact interactions of the emulsion components with the surface of the filter elements. The materials used in the oil and oil refining industry and in contact with an aggressive environment, such as crude oil, are also subject to the requirements of chemical resistance, mechanical strength, thermal stability and environmental safety. In addition, polymeric materials intended for the manufacture of injection molded products must have high melt flow (low viscosity). This is a prerequisite for the production of coalescing partitions or plates of a coalescing package of a separator of oil-water or oil-water mixture, which are thin-walled products having a thickness of 1.0-1.3 mm. The polymer material for the plates of the coalescing package of the separator of the oil-water or oil-water mixture should also have heat resistance, since during operation of the bag the space between the plates is clogged with oil or oil over time, and its cleaning is carried out using sharp steam having a temperature of 130-140 ° C.

To the highest degree, the filled polypropylene-based compositions may meet the above requirements. It should be noted that the use of fillers is the most widely used method of modifying the properties of polypropylene, which allows to increase strength, hardness, stiffness, heat resistance, frost resistance, wear resistance during abrasion, dimensional stability and improve other properties important when using polypropylene as a structural material. The main requirements for fillers for propylene are: low density, chemical purity and high brightness, low absorption capacity, a narrow range of particle sizes (usually from 1 to 15 microns), cheapness (Ivanyukov D.V., Fridman M. L. Polypropylene / properties and application /. - M .: Chemistry, 1974, p. 125).

Known polypropylene molding mixture for the manufacture of shaped parts with a decorative surface (RF patent No. 2154657, IPC ⁷ C 08 L 23/12, publ. 08/20/2000), including: a) 85-50 wt.% Of isotactic polypropylene or copolymers of propylene with almost up to 10 wt.% ethylene; b) 5-30 wt.% rubbery, compatible with polypropylene copolymers; c) 10-40 wt.% reinforcing fillers and 0.3-3 wt.% calculated on a) + b) + c) carbon fibers with a fiber length of 0.5-18 mm. Talc, chalk, fiberglass or glass beads are preferably used as reinforcing fillers.

The technical result of the known composition is the creation of a material which, by injection molding, leads to shaped parts having a similar textile appearance and intended for use in the passenger compartment. Known material has high heat resistance, high strength, but it is not suitable for the manufacture of coalescing baffles or plates of a coalescing emulsion separator package, since its inherent rheological properties (high viscosity) do not allow the manufacture of thin-walled products from it, and insufficient chemical resistance makes it impossible to use it in aggressive environments in view of the presence in its composition of fibers whose intermolecular physical interaction with polypropylene is insufficient exact process to prevent intermolecular diffusion of crude oil or oil arising in the operation of the product, and which will inevitably lead to physical degradation, and as a result - in the loss of material and the physical and mechanical performance properties.

Known polymer composition (patent RU No. 2030427, IPC ⁶ C 08 L 23/12, C 08 K 13/02, publ. 10.03.95), including: 52.0-72.5 wt.% Polypropylene, 20-40 wt. .% inorganic filler, 3-5 wt.% high-pressure polyethylene, 2.4-2.6 wt.% calcium stearate, 0.4-0.6 wt.% polyhydrosiloxane fluid and intended for the manufacture of products for various purposes (containers, furniture, etc.) by injection molding.

The known composition has relatively low indicators of physical and mechanical properties, which, along with its inherent low indicators of heat resistance, chemical resistance and melt flow (MFR), does not allow the use of this polymer composition for the manufacture of coalescing baffles or plates of a coalescing emulsion separator package.

The objective of the invention is to create a material suitable for processing into products by injection molding and having an improved set of physicomechanical, thermophysical, chemical and operational properties, allowing it to be used for the manufacture of coalescing baffles or plates of a coalescing emulsion separator package.

This object is achieved in that the polypropylene composite material for the emulsion separator contains polypropylene having a melt flow rate of 3-6 g / 10 min, polypropylene having a melt flow rate of 13-25 g / 10 min, a finely divided inorganic filler, which is marble flour, stabilizing additive in the form of 3,5-di-tert-butyl-4-hydroxyphenyl propionic acid ester and pentaerythritol, and technological additives — zinc stearate and paraffin oil in the following ratio, wt.%:

flow index polypropylene

melt 3-6 g / 10 min 50-60

flow index polypropylene

melt 13-25 g / 10 min 20-30

marble flour 16-18

zinc stearate 1.2-1.8

Vaseline oil 1.0-1.3

3,5-di-tert-butyl-4-hydroxyphenyl ether

propionic acid and pentaerythritol 0.8-1.0

The proposed polypropylene composite material has good strength characteristics (tensile strength 28-34 MPa, elongation 90-110%, Brinell hardness 51-55 MPa), and also has high heat resistance (Martens heat resistance 105-111 ° C) and chemical resistance (1 point), high fluidity in the melt (melt flow rate / MFR / is 11-14 g / 10 min at a temperature of T = 230 ° C and a load of P = 21.2 N), Its composition provides the ability to obtain modern materials highly efficient and economically viable different equipment according to a one-stage technological scheme, does not lead to wear of plasticizing equipment, does not require expensive forming equipment.

It was found that the presence in the composition of the material of 50-60 wt.% Polypropylene having a PTR of 3-6 g / 10 min, and 20-30 wt.% Of polypropylene having a PTR of 13-25 g / 10 min, provides them with stirring in the melt the formation of a homophasic structure of the polymer matrix for a fine filler in the form of marble flour, taken in an amount of 16-18 wt.%, which leads to the formation of a monolithic composite material that can actively counteract the energy and chemical effects. Given the propensity of polypropylene to thermal oxidative degradation, 3,5-di-tert-butyl-4-hydroxyphenyl propionic acid and pentaerythritol ester in the amount of 0.8-1.0 wt.%, Which contributes to an increase in the resistance of the material to destruction under load when heated to temperatures exceeding 120 ° C, that is, resistance to physical destruction. Technological additives: zinc stearate in an amount of 1.2-1.8 wt.% And liquid paraffin in an amount of 1.0-1.3 wt.% Are designed to ensure the effective operation of plasticizing equipment when conducting the technological process of material formation, as they prevent the product from sticking to the surface of the forming tool.

In the study of the prior art, no similar compositions of polymeric materials were found that would be characterized by an identical set of essential features with the achievement of the same technical result as obtained in the claimed solution, which allows us to conclude that it meets the criteria of "novelty" and "inventive step". The proposed technical solution can be made industrially from known materials using known technical means, which indicates its compliance with the criterion of "industrial applicability".

The invention is illustrated by the following examples.

Example 1

The polypropylene composite material for the emulsion separator is produced on a Werner and Pfleider two-screw mixer-granulator with a productivity of 800 kg / h, producing granules of the same geometric shape within one batch, the size of which in any direction is 2-5 mm. Before feeding into the loading hopper of the mixer-granulator, the components that make up the material are mixed in the required ratio in a container suitable for mixing and mixed thoroughly for 5-10 minutes to homogenize the mixture.

To prepare 100 kg of the mixture, take 60 kg (60 wt.%) Of 21060 grade polypropylene (PTR = 6 g / 10 min at a temperature of T = 230 ° C and a load of P = 21.2 N) according to GOST 29996-86; 20 kg (20 wt.%) Of grade 21130 polypropylene (PTR = 13 g / 10 min at a temperature of T = 230 ° C and a load of P = 21.2 N) according to GOST 29996-86; 16 kg (16 wt.%) Of marble flour AMИAKAP-2GU brand (producer Finland) with a particle size of 2-6 microns; 1.8 kg (1.8 wt.%) Zinc stearate (TU 6-09-17-279-88); 1.2 kg (1.2 wt.%) Of liquid paraffin (GOST 3164-78) and 1.0 kg (1 wt.%) Of 1010 grade Irganox (a product of SIBA, Switzerland), which is a 3,5-di ester tert-butyl-4-hydroxyphenyl propionic acid and pentaerythritol.

Examples 2-5.

The technology for obtaining the material is similar to example 1, the differences are in the quantitative content of the components of the material, as well as in the fact that in examples 2 and 4 polypropylene grade 21040 (PTR = 4 g / 10) was used as a polypropylene with a flow rate of 3-6 g / 10 min min at a temperature of T = 230 ° C and a load of P = 21.2 N) according to GOST 29996-86, in examples 3 and 5 - polypropylene grade 21030 (PTR = 3 g / 10 min at a temperature of T = 230 ° C and a load of P = 21.2 N) according to GOST 29996-86, and polypropylene grade 21250 (MFR = 25 g /) was used as polypropylene with a yield strength of 13-25 g / 10 min in examples 2 and 4 10 min at a temperature of T = 230 ° C and a load of P = 21.2 N) according to GOST 29996-86, in examples 3 and 5 - grade 21180 polypropylene (PTR = 18 g / 10 min at a temperature of T = 230 ° C and a load P = 21.2 N) according to GOST 29996-86.

The compositions of the polypropylene material according to examples 1-5 are shown in table 1.

Samples of the obtained composite material according to examples 1-5 were subjected to standard tests and determined the strength properties (tensile strength and elongation at break) of the material according to GOST 11262; Brinell hardness according to GOST 4670; chemical resistance according to GOST 12020-72; heat resistance according to Martens (V.K. Kryzhanovsky, V. V. Burlov. Applied Physics of Polymer Materials. St. Petersburg, 2001, p. 149); melt flow rate (MFR) according to GOST 11645 using an IIRT-M2 capillary viscometer under standard conditions for polypropylene (T = 230 ° C, P = 21.2 N). The test results are shown in table 2.

As can be seen from table 2, obtained in examples 1-3 polypropylene material has an improved set of properties. When leaving the claimed area of the quantitative content of the components of the material (examples 4,5), the properties of the material deteriorate (strength becomes lower, the rheological properties of the material and its chemical resistance deteriorate).

The properties of the obtained polypropylene composite material allow us to conclude that the claimed material is suitable for injection molding of coalescing baffles or plates of a coalescing emulsion separator package, since it is characterized by good strength, high heat resistance and chemical resistance, high melt flow. Its composition provides the opportunity to obtain material on modern highly efficient and economically feasible equipment according to a one-stage technological scheme, does not lead to wear of plasticizing equipment, does not require expensive forming equipment.

Table 1 MATERIAL COMPOSITION NO PRI ME PA POLYPROPYLENE with a melt flow rate of 3-6 g / 10 min, wt.% POLYPROPYLENE with a melt flow rate of 13-25 g / 10 min, wt.% finely divided inorganic FILLER, wt.% TECHNOLOGICAL ADDITIVE, wt.% STABILIZING ADDITIVE, wt.% 1 60 twenty marble flour
16 zinc stearate
1.8 Vaseline oil
1,2 irganox 1010
1,0 2 52 26 marble flour
18 zinc stearate
1.7 Vaseline oil
1.3 irganox 1010
1,0 3 fifty thirty marble flour
17 zinc stearate
1,2 Vaseline oil
1,0 irganox 1010
0.8 4* 64 eighteen marble flour
14 zinc stearate
1,1 Vaseline oil
1.4 irganox 1010
1,5 5* 45 32 marble flour
twenty zinc stearate
2.0 Vaseline oil
0.5 irganox 1010
0.5 * examples outside the claimed field

table 2 PHYSICAL-MECHANICAL AND RHEOLOGICAL PROPERTIES OF POLYPROPYLENE COMPOSITE MATERIAL EXAMPLE NO. Tensile Strength, MPa RELATIVE elongation at break,% HARDNESS BY BRINELL, MPa HEAT RESISTANCE BY MARTENS, ° С CHEMICAL RESISTANCE, points Melt Flow Rate (T = 230 ° C, P = 21.2 H) g / 10 min 1 28-30 110 51 105 1 eleven 2 29-31 100 52 111 1 12 3 32-34 90 55 108 1 14 4* 24-26 130 46 90 2 nine 5* 20-24 90 60 98 3 16 * examples outside the claimed field

Claims (1)

A polypropylene composite material for an emulsion separator, including polypropylene having a melt flow rate of 3-6 g / 10 min, and polypropylene having a melt flow rate of 13-25 g / 10 min, a finely divided inorganic filler, which is a marble flour, stabilizing the additive in the form 3,5-di-tert-butyl-4-hydroxyphenyl propionic acid ester and pentaerythritol, and processing aids — zinc stearate and paraffin oil in the following ratio, wt.%: flow index polypropylene melt 3-6 g / 10 min 50-60 flow index polypropylene melt 13-25 g / 10 min 20-30 marble flour 16-18 zinc stearate 1.2-1.8 Vaseline oil 1.0-1.3 3,5-di-tert-butyl-4-hydroxyphenyl ester propionic acid and pentaerythritol 0.8-1.0