CN113583167A - Device and method for producing propylene-butylene random copolymerization polypropylene by gas phase process - Google Patents
Device and method for producing propylene-butylene random copolymerization polypropylene by gas phase process Download PDFInfo
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- CN113583167A CN113583167A CN202110998244.3A CN202110998244A CN113583167A CN 113583167 A CN113583167 A CN 113583167A CN 202110998244 A CN202110998244 A CN 202110998244A CN 113583167 A CN113583167 A CN 113583167A
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- 238000000034 method Methods 0.000 title claims abstract description 42
- -1 propylene-butylene Chemical group 0.000 title claims abstract description 40
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 28
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 80
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 61
- 238000001035 drying Methods 0.000 claims abstract description 56
- 238000003860 storage Methods 0.000 claims abstract description 56
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 25
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005469 granulation Methods 0.000 claims abstract description 24
- 230000003179 granulation Effects 0.000 claims abstract description 24
- 238000007872 degassing Methods 0.000 claims abstract description 20
- 238000001125 extrusion Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 77
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052785 arsenic Inorganic materials 0.000 claims description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010963 304 stainless steel Substances 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 229920005675 propylene-butene random copolymer Polymers 0.000 claims 1
- 239000000047 product Substances 0.000 description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- 238000005453 pelletization Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 9
- 238000007670 refining Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 238000012986 modification Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GNQIYVVJPHCTPZ-UHFFFAOYSA-N buta-1,3-diene propane Chemical compound CCC.C=CC=C GNQIYVVJPHCTPZ-UHFFFAOYSA-N 0.000 description 2
- 230000005465 channeling Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000008029 phthalate plasticizer Substances 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
Abstract
The invention discloses a propylene-butylene random copolymerization polypropylene production device by a gas phase process, which comprises the following steps: a propylene storage tank and a butylene storage tank; the device comprises a propylene storage tank, a solid alkali drying tank, a propylene degassing tower, a primary drying tank, a desulfurizing tower, an dearsenization tower, a deaMAP tower, a secondary drying tank and a reactor, wherein the propylene storage tank is connected with the solid alkali drying tank, the solid alkali drying tank is connected with the propylene degassing tower, the propylene degassing tower is connected with the primary drying tank, the primary drying tank is connected with the desulfurizing tower, the desulfurizing tower is connected with the dearsenization tower, the dearsenization tower is connected with the MAP removal tower, the MAP removal tower is connected with the secondary drying tank, and the secondary drying tank is connected with the reactor; the butene storage tank is connected with the dryer, the dryer is connected with the butene filter, the butene filter is connected with the circulating gas cooler, and the circulating gas cooler is connected with the reactor; the reactor is connected with a circulating gas compressor, the circulating gas compressor is connected with a circulating gas cooler, and the circulating gas cooler is connected with the reactor; the reactor is connected with a powder purifying bin, and the powder purifying bin is connected with an extrusion granulation system; an on-line gas chromatographic analyzer is arranged in the reactor. Is convenient for the production of propylene-butylene random copolymerization polypropylene products.
Description
Technical Field
The invention relates to the technical field of polypropylene production, in particular to a device and a method for producing propylene-butylene random copolymerization polypropylene by a gas phase process.
Background
Polypropylene has become the fastest growing and most actively developed new product of five general synthetic resins because of its outstanding mechanical properties, lower density, superior electrical insulation properties and excellent processability. The homopolymerized polypropylene has higher isotacticity and crystallinity, and optical property deviations such as product glossiness and transparency, and the like, and has limited development in the fields of high-end daily necessities and exquisite packaging due to lower impact strength. The random copolymerization polypropylene is a common on-line modification method for changing the mechanical property and the optical property of polypropylene by introducing a second monomer or a third monomer into the polypropylene macromolecular chain structure to destroy the crystal structure. Ethylene is the most commonly used second monomer in the industry, and the reports of producing different types of random copolymerization products by introducing ethylene are more, but in the field of transparent polypropylene, the small molecular chains of ethylene are smaller, so that the small molecular precipitates of the final product are more and heavier in smell, the surface printing is influenced, and the food safety hidden danger is easy to exist. Thus, propylene-butylene copolymer polypropylene produced by random copolymerization by introducing butene having a relatively long molecular chain as a second monomer has recently been a hot spot of research and development.
At present, most of the propylene-butadiene copolymer products in the market are produced by a Spheripol double-loop process CN104479228A and CN111100382A, a horizontal double-reactor Inovene process CN106084488A and a batch-method liquid-phase small body process CN110724219A, the problems of low content of low-molecular precipitates, poor heat resistance and the like are solved, but the production is basically completed by connecting two or more reactors in series, a primary product is obtained by a first reactor, a secondary product is obtained by a second reactor, the operation is more complicated, the retention time of the product is longer, the efficiency is low, and systems such as a butene storage tank, butene refining and the like are required to be independently equipped. For the field of special materials for the propane-butadiene copolymerization with small market demands, in order to produce a small amount of required propane-butadiene copolymerization products, additionally arranged equipment is high in investment, high in cost and low in utilization rate.
The Unipol gas-phase fluidized bed polypropylene process is still in the technical digestion period at present, and the patent technical report of the technology in the field related to the polypropylene copolymer of propylene and butylene is not searched.
Disclosure of Invention
The invention aims to provide a device and a method for producing propylene-butylene random copolymerization polypropylene by a gas phase process. Based on the Unipol gas phase fluidized bed process technology of the single reactor, provide a convenient production method, the unique advantage of this method lies in: only on the basis of the traditional ethylene-propylene copolymerization reaction system, the operation method is improved, and the production of the propylene-butylene copolymerization product can be realized under the condition of not increasing a butylene storage tank, a refining system and an analysis module; only a single reactor is used, so that the operation is simple and the cost is saved; the special material for the polypropylene copolymer is green, environment-friendly, free of any plasticizer, low in haze and controllable and adjustable in product performance parameters.
In order to solve the technical problems, the invention adopts the following technical scheme:
a gas phase process propylene-butylene random copolymerization polypropylene production device comprises: a propylene storage tank and a butylene storage tank;
the device comprises a propylene storage tank, a solid alkali drying tank, a propylene degassing tower, a primary drying tank, a desulfurizing tower, an dearsenization tower, a deaMAP tower, a secondary drying tank and a reactor, wherein the propylene storage tank is connected with the solid alkali drying tank, the solid alkali drying tank is connected with the propylene degassing tower, the propylene degassing tower is connected with the primary drying tank, the primary drying tank is connected with the desulfurizing tower, the desulfurizing tower is connected with the dearsenization tower, the dearsenization tower is connected with the MAP removal tower, the MAP removal tower is connected with the secondary drying tank, and the secondary drying tank is connected with the reactor;
the butene storage tank is connected with the dryer, the dryer is connected with the butene filter, the butene filter is connected with the circulating gas cooler, and the circulating gas cooler is connected with the reactor;
the reactor is connected with a circulating gas compressor, the circulating gas compressor is connected with a circulating gas cooler, and the circulating gas cooler is connected with the reactor;
the reactor is connected with a powder purifying bin, and the powder purifying bin is connected with an extrusion granulation system;
an on-line gas chromatographic analyzer is arranged in the reactor.
Further, the method comprises the following steps of; the method comprises the following steps:
a: propylene in a propylene storage tank firstly enters a solid alkali drying tank to remove free water therein, then enters a propylene degassing tower to ensure that light component gas in the discharge material at the bottom of the propylene degassing tower enters a primary drying tank to further remove water therein, then enters a desulfurizing tower to remove sulfur content therein, then sequentially passes through an arsenic removing tower and a MAP removing tower to sequentially remove arsenic, phosphorus, methylacetylene and propadiene therein, and finally enters a secondary drying tank, and is dried and then enters a reactor;
b: liquid butylene in the butylene storage tank directly enters from the bottom of the dryer, is discharged from the top, is respectively removed of impurities such as sulfur, water and the like, is filtered by a butylene filter to remove pollutant particles, and then is sent to a circulating gas cooler to enter into the reactor;
c: and C, reacting the propylene in the step A with the butylene in the step B in a reactor, injecting a catalyst, an electron donor and a cocatalyst into the reactor, performing a circulating reaction on materials in the reactor among the reactor, a circulating gas compressor and a circulating gas cooler during the reaction, feeding a product after the reaction into a powder purifying bin, removing the catalyst which is not completely reacted in the powder purifying bin, and feeding the product and a specific additive into an extrusion granulation system for granulation.
Further, the method comprises the following steps of; in the step C, the reactor is a single fluidized bed reactor, a catalyst, an electron donor and a cocatalyst are injected into the reactor, the catalyst is Consista602, the electron donor is D9600, and the cocatalyst is triethylaluminum;
controlling the condensation capacity of the reactor to be not less than 6%.
Further, the method comprises the following steps of; in the step B, 50kg/h of butylene is slowly added, the adding speed of the butylene is controlled to be 30-40kg/15min, and the dew point temperature difference of the bed is controlled to be less than or equal to 3.0 ℃.
Further, the method comprises the following steps of; in the step C, the mole of hydrogen and carbon in an H2/C3 reactor is the mole ratio of hydrogen to a propylene monomer, the mole ratio of C4/C3 is the mole ratio of butylene to the propylene monomer, and the mole ratio of Al/Si serving as a cocatalyst, triethyl aluminum and an electron donor D9600 is stably controlled;
the calculation of C4/C3 was carried out by an indirect difference method using an on-line gas chromatograph which measures the propylene, propane, hydrogen and nitrogen components in the recycle gas.
Further, the method comprises the following steps of; the molar ratio of H2/C3 is 0.014-0.065, the molar ratio of C4/C3 is 0.02-0.06, and the molar ratio of Al/Si is 4-11.
Further, the method comprises the following steps of; the propylene storage tank and the butylene storage tank are made of 304 stainless steel, the designed temperature range of the propylene storage tank and the butylene storage tank is-196 ℃ to 50 ℃, and the bearing pressure is 0.84 MpaG.
Further, the method comprises the following steps of; the extrusion granulation system adopts an underwater granulation system, the feed pressure is 3-5 Mpa, the temperature of the granulation water is 40-60 ℃, the opening of the throttle valve is 20-40 ℃, the rotating speed of the granulator is 600-1000rpm, and the pressure of the inlet of the melting pump is 1-3 Mpa.
Further, the method comprises the following steps of; in the step C, specific additives in the extrusion granulation system comprise an antioxidant Irganox-1010, an antioxidant Irgafos-168, an acid scavenger, a release agent and a transparent nucleating agent.
Further, the method comprises the following steps of; in the step A, the partial pressure of propylene is gradually reduced to 2.2Mpa at the rate of 0.06Mpa/h, and the temperature of the reactor is gradually reduced to 64 ℃ at the rate of 0.03-0.1 ℃/min.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. the range of the melt index of the prepared propane-butadiene copolymer product is controllable within 3-65g/10min, the flexural modulus is larger than or equal to 900Mpa, the haze is smaller than or equal to 10%, the ash content is smaller than or equal to 250ppm, and the product does not contain phthalate plasticizer, so that the related detection requirements of national food safety are met.
2. The production method of the propylene-butylene copolymer product is characterized in that the propylene-butylene copolymer product is produced by modifying a traditional ethylene-propylene copolymer production device system and then sharing one system, and the production operation of the propylene-butylene copolymer product is convenient and fast under the condition that a butylene storage tank, a refining system and an analysis module are not added at all, and comprises the following steps: (1) the storage and pumping of the butylene uses an original ethylene tank area system, an ethylene storage tank is used for storing the butylene, and a butylene tank area is not newly added; (2) the original ethylene refining system is subjected to micro-modification to meet the butene refining requirement; (3) after being refined, propylene and butylene are pushed by a circulating gas compressor to carry out random copolymerization in a gas-phase fluidized bed reactor to obtain a propylene-butylene copolymer base stock; (4) and mixing the base material with various auxiliaries, and carrying out underwater dicing to obtain a final product.
3. The method is characterized in that a butylene refining system is not additionally arranged, a raw ethylene refining system is directly used, but because ethylene is fed in a gas mode and butylene is fed in a liquid mode, the flowing direction of the purified butylene is kept from bottom to top, and the operation is opposite to that of raw ethylene, so that liquid channeling is avoided. As the butylene is fed by liquid, the butylene cannot be injected into the reaction system before the circulating gas compressor like ethylene so as to prevent the liquid from entering the compressor to cause the damage of the compressor, and therefore, a pipeline needs to be newly added to inject the butylene into the reaction system after crossing the circulating gas compressor.
Drawings
FIG. 1 is a schematic view of the structure of the present invention.
In the figure: the system comprises a propylene storage tank 1, a butene storage tank 2, a solid caustic soda drying tank 3, a propylene degassing tower 4, a primary drying tank 5, a desulfurizing tower 6, an arsenic removing tower 7, a MAP removing tower 8, a secondary drying tank 9, a reactor 10, a dryer 11, a butene filter 12, a circulating gas cooler 13, a circulating gas compressor 14, a powder purifying bin 15, an extrusion granulation system 16 and an online gas chromatography analyzer 17.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments, as shown in fig. 1. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
a gas phase process propylene-butylene random copolymerization polypropylene production device comprises: a propylene storage tank 1 and a butylene storage tank 2;
the method comprises the following steps that a propylene storage tank 1 is connected with a solid alkali drying tank 3, the solid alkali drying tank 3 is connected with a propylene degassing tower 4, the propylene degassing tower 4 is connected with a primary drying tank 5, the primary drying tank 5 is connected with a desulfurizing tower 6, the desulfurizing tower 6 is connected with an arsenic removing tower 7, the arsenic removing tower 7 is connected with an MAP removing tower 8, the MAP removing tower 8 is connected with a secondary drying tank 9, and the secondary drying tank 9 is connected with a reactor 10;
the butene storage tank 2 is connected with a dryer 11, the dryer 11 is connected with a butene filter 12, the butene filter 12 is connected with a circulating gas cooler 13, and the circulating gas cooler 13 is connected with the reactor 10;
the reactor 10 is connected with a circulating gas compressor 14, the circulating gas compressor 14 is connected with a circulating gas cooler 13, and the circulating gas cooler 13 is connected with the reactor 10;
the reactor 10 is connected with a powder purifying bin 15, and the powder purifying bin 15 is connected with an extrusion granulation system 16;
an online gas chromatographic analyzer 17 is arranged in the reactor 10; the system comprises a propylene storage tank 1, a butene storage tank 2, a solid alkali drying tank 3, a propylene degassing tower 4, a primary drying tank 5, a desulfurizing tower 6, an arsenic removing tower 7, an MAP removing tower 8, a secondary drying tank 9, a reactor 10, a dryer 11, a butene filter 12, a circulating gas cooler 13, a circulating gas compressor 14 and a powder purifying bin 15, wherein the parts needing to be connected of the powder purifying bin 15 and an extrusion granulation system 16 are connected by adopting pipelines, and the pipelines are provided with corresponding power pumps; propylene in a propylene storage tank 1 enters a solid alkali drying tank 3 for drying, the solid alkali drying tank 3 is dried and then enters a propylene degassing tower 4, the propylene degassing tower 4 is connected with a primary drying tank 5, the primary drying tank 5 is connected with a desulfurizing tower 6 for further drying, the desulfurizing tower 6 is connected with a dearsenifying tower 7, the dearsenifying tower 7 is connected with a MAP-removing tower 8, the MAP-removing tower 8 is connected with a secondary drying tank 9, and the secondary drying tank 9 is connected with a reactor 10; the butylene storage tank 2 is dried, filtered and cooled by a dryer 11, a butylene filter 12 and a circulating gas cooler 13 and then enters a reactor 10; the gas is analyzed in the on-line gas chromatograph 17, and the content of propylene or butene is supplemented as necessary. A closed loop system is formed among the reactor 10, the circulating gas cooler 13 and the circulating gas compressor 14, and the inside of the reactor is ensured to be in a fluidized state. Butene is fed as a liquid, so the flow direction should be maintained from bottom to top as butene is refined, as opposed to raw ethylene operation, to avoid liquid channeling. The production device is a Unipol process technology, originally can only be an ethylene-propylene copolymerization system, and does not have a propylene-butylene copolymerization and butylene refining system. After the transformation, the original ethylene storage tank is used for storing the butylene raw material, and the butylene process flow of the ethylene refining system after the transformation is as follows: the liquid butylene directly enters from the bottom of the butylene drying tank 11, is discharged from the top, is respectively removed of sulfur, water and other impurities, and then is sent to a reaction system after being filtered by an ethylene filter 12 to remove pollutant particles.
Example 2:
on the basis of the embodiment 1, the method comprises the following steps:
the method comprises the following steps:
a: propylene in a propylene storage tank 1 firstly enters a solid alkali drying tank 3 to remove free water therein, then enters a propylene degassing tower 4, so that light component gas in the discharge material at the bottom of the propylene degassing tower 4 enters a primary drying tank 5 to further remove water therein, then enters a desulfurizing tower 6 to remove sulfur content therein, then sequentially removes arsenic, phosphorus, methylacetylene and propadiene therein through a dearsenification tower 7 and a MAP removal tower 8, and finally enters a secondary drying tank 9, and is dried and then enters a reactor 10; propylene in the propylene storage tank 1 firstly enters a solid alkali drying tank 3 to remove free water therein and then enters a propylene degassing tower 4, so that light component gas H in the bottom discharge of the tower2，O2，CO，CO2The content is less than 0.1 ppm. The propylene enters a propylene primary drying tank 5 after being degassed, and the moisture in the propylene is further removed, so that the moisture content at the outlet is reduced to be below 6 ppm. Then the product enters a propylene desulfurization tank 5 to remove the sulfur content in the product, so that the total sulfur content at the outlet is reduced to below 0.1 ppm; then sequentially passes through a propylene dearsenifying tank 7 and propylene MThe AP tower 8 removes arsenic in sequence<0.1ppm, phosphorus and methylacetylene<0.1ppm of propadiene<After 0.1PPm, it finally enters the secondary drying tank 9 for propylene, after which the water content in the outlet is reduced to below 0.1PPm, and enters the reactor 10 via the circulating gas line.
B: the liquid butylene in the butylene storage tank 2 directly enters from the bottom of the dryer 11, is discharged from the top, is respectively removed of sulfur, water and other impurities, is filtered by a butylene filter 12 to remove pollutant particles, and then is sent to a circulating gas cooler 13 to enter into the reactor 10; the method comprises the steps of pressing butylene from a tank car into a butylene storage tank 2 by using low-pressure nitrogen, enabling the butylene in the butylene storage tank 2 to enter a dryer 11 for drying, respectively removing impurities such as sulfur, water and the like in the butylene storage tank, filtering by a butylene filter 12, filtering the butylene by an ethylene filter 12 to remove pollutant particles, then entering a circulating gas cooler 13 for cooling, and then sending to a reaction system.
C: the propylene in the step A and the butylene in the step B react in a reactor 10, a catalyst, an electron donor and a cocatalyst are injected into the reactor 10, materials in the reactor 10 carry out a circulating reaction among the reactor 10, a circulating gas compressor 14 and a circulating gas cooler 13 during the reaction, a product after the reaction enters a powder purifying bin 15, the catalyst which is not completely reacted is removed in the powder purifying bin 15, and then the product and a specific additive enter an extrusion granulation system 16 for granulation; the preparation of the product is convenient.
Example 3:
on the basis of the embodiment 1-2, in the step C, the reactor 10 is a single fluidized bed reactor, a catalyst, an electron donor and a cocatalyst are injected into the reactor 10, wherein the catalyst is Consista602, the electron donor is D9600, and the cocatalyst is triethylaluminum; controlling the condensation capacity of the reactor 10 to be not less than 6%;
controlling the condensation capacity of the reactor 10 to be not less than 6%; the electron donor D9600 belongs to the silane class and is alkoxy silane RnSi (OR ') 4-n, wherein n =1-4, R = C6H5, R' = C1-3-alkyl; the catalyst is Consista602, the electron donor is D9600, and the cocatalyst is triethylaluminum, so that the reaction of propylene and butylene is facilitated, and the condensation amount is controlled and the reaction is facilitated.
Example 4:
on the basis of the embodiments 1 to 3, in the step B, 50kg/h of butylene is slowly added, the adding speed of the butylene is controlled to be 30 to 40kg/15min, and the dew point temperature difference of a bed is controlled to be less than or equal to 3.0 ℃; the control of the entering speed of the butylene is convenient for the reaction and the quality of the reaction product to meet the requirement.
Example 5:
on the basis of the examples 1-4, the molar ratio of hydrogen to carbon in the H2/C3 reactor is the molar ratio of hydrogen to propylene monomer, the molar ratio of C4/C3 is the molar ratio of butylene to propylene monomer, and the molar ratio of Al/Si as a cocatalyst, triethyl aluminum and an electron donor D9600 is stably controlled;
the calculation of C4/C3 is obtained by adopting an indirect difference method after the online gas chromatographic analyzer 17 outputs the numerical values of the components of propylene, propane, hydrogen and nitrogen in the circulating gas; the H2/C3, C4/C3 and Al/Si in the reactor 10 are monitored by an online gas chromatograph 12 to facilitate the reaction.
Example 6:
based on examples 1-5, the molar ratio H2/C3 was 0.014, the molar ratio C4/C3 was 0.02, and the molar ratio Al/Si was 4; a closed loop system is formed among the reactor 10, the circulating gas cooler 13 and the circulating gas compressor 14, and the closed loop system is stable, so that the inside of the reactor is in a fluidized state.
Example 7:
based on examples 1-6, the molar ratio H2/C3 was 0.065, the molar ratio C4/C3 was 0.06, and the molar ratio Al/Si was 11; a closed loop system is formed among the reactor 10, the circulating gas cooler 13 and the circulating gas compressor 14, and the closed loop system is stable, so that the inside of the reactor is in a fluidized state.
Example 8:
based on examples 1-7, the molar ratio H2/C3 was 0.042, the molar ratio C4/C3 was 0.04, and the molar ratio Al/Si was 7.5; the circulating gas compressor 8, the second cooler 9 and the reactor 10 are convenient to form a closed loop system, and the closed loop system is stable, so that the inside of the reactor is in a fluidized state.
Example 9:
on the basis of the embodiment 1-8, the storage tanks of the propylene storage tank 1 and the butylene storage tank 2 are made of 304 stainless steel, the design temperature range of the propylene storage tank 1 and the butylene storage tank 2 is-196 ℃ to 50 ℃, and the bearing pressure is 0.84 MpaG; the storage of propylene and butylene is convenient.
Example 10:
on the basis of the embodiments 1 to 9, the extrusion granulation system 16 is an underwater pelletizing system, the feed pressure is 3 Mpa, the pelletizing water temperature is 40 ℃, the opening degree of a throttle valve is 20 degrees, the rotating speed of a pelletizer is 600rpm, and the inlet pressure of a melting pump is 1 to 3 Mp; the underwater pelletizing system of the extrusion pelletizing system 16 is controlled, so that the prepared product can meet the requirement conveniently.
Example 11:
on the basis of the embodiments 1 to 10, the extrusion granulation system 16 is an underwater pelletizing system, the feed pressure is 5 Mpa, the pelletizing water temperature is 60 ℃, the opening degree of a throttle valve is 40 ℃, the rotating speed of a pelletizer is 1000rpm, and the inlet pressure of a melting pump is 1 to 3 Mp; the underwater pelletizing system of the extrusion pelletizing system 16 is controlled, so that the prepared product can meet the requirement conveniently.
Example 12:
on the basis of the examples 1 to 11, the extrusion granulation system 16 is an underwater pelletizing system, the feed pressure is 4Mpa, the pelletizing water temperature is 50 ℃, the opening degree of a throttle valve is 30 degrees, the rotating speed of a pelletizer is 800rpm, and the inlet pressure of a melting pump is 2 Mp; the underwater pelletizing system of the extrusion pelletizing system 16 is controlled, so that the prepared product can meet the requirement conveniently.
Example 13:
in step C, specific additives for extrusion granulation system 16 include Irganox-1010 antioxidant, Irgafos-168 antioxidant, acid scavenger, mold release agent, and transparent nucleating agent, based on examples 1-12. The addition of the additive is convenient for granulating.
Example 14:
based on examples 1 to 13, in step A, the partial pressure of propylene was gradually decreased to 2.2MPa at a rate of 0.06MPa/h, and the reactor temperature was gradually decreased to 64 ℃ at a rate of 0.03 to 0.1 ℃/min; after the addition of the butene, the balance in the original reactor is destroyed, local overheating reaction is easily caused, and caking is caused, so that the addition of the butene is facilitated by reducing the point reaction temperature.
Example 15:
based on examples 1-14, the molar ratio H2/C3 was 0.014, the molar ratio C4/C3 was 0.028, and the molar ratio Al/Si was 4; a closed loop system is formed among the reactor 10, the circulating gas cooler 13 and the circulating gas compressor 14, and the closed loop system is stable, so that the inside of the reactor is in a fluidized state.
Example 16:
based on examples 1-15, the molar ratio H2/C3 was 0.042, the molar ratio C4/C3 was 0.058, and the molar ratio Al/Si was 4; a closed loop system is formed among the reactor 10, the circulating gas cooler 13 and the circulating gas compressor 14, and the closed loop system is stable, so that the inside of the reactor is in a fluidized state.
Example 17:
based on examples 1-16, the molar ratio H2/C3 was 0.065, the molar ratio C4/C3 was 0.05, and the molar ratio Al/Si was 6.0; a closed loop system is formed among the reactor 10, the circulating gas cooler 13 and the circulating gas compressor 14, and the closed loop system is stable, so that the inside of the reactor is in a fluidized state.
Example 18:
based on examples 1-17, the molar ratio H2/C3 was 0.065, the molar ratio C4/C3 was 0.06, and the molar ratio Al/Si was 10; a closed loop system is formed among the reactor 10, the circulating gas cooler 13 and the circulating gas compressor 14, and the closed loop system is stable, so that the inside of the reactor is in a fluidized state.
The polypropylene product obtained in the application has the controllable melt index range of 3-65g/10min, the bending modulus of more than or equal to 900MPa, the haze of less than or equal to 10 percent and the ash content of less than or equal to 250ppm, does not contain phthalate plasticizer, and meets the related detection requirements of national food safety.
Table 1 table of product quality of examples
As can be seen from Table 1, the propylene-butylene copolymer product produced by the method has the advantages of wide controllable ranges of melt index, xylene soluble content and mechanical property, low haze and all indexes superior to the industrial standard.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.
Claims (10)
1. A gas phase process propylene-butylene random copolymerization polypropylene production device is characterized in that: the method comprises the following steps: a propylene storage tank (1) and a butylene storage tank (2);
the device comprises a propylene storage tank (1), a solid alkali drying tank (3), a propylene degassing tower (4), a primary drying tank (5), a desulfurizing tower (6), an arsenic removing tower (7), an MAP removing tower (8), a secondary drying tank (9), and a reactor (10), wherein the propylene storage tank (1) is connected with the solid alkali drying tank (3);
the butene storage tank (2) is connected with the dryer (11), the dryer (11) is connected with the butene filter (12), the butene filter (12) is connected with the circulating gas cooler (13), and the circulating gas cooler (13) is connected with the reactor (10);
the reactor (10) is connected with a recycle gas compressor (14), the recycle gas compressor (14) is connected with a recycle gas cooler (13), and the recycle gas cooler (13) is connected with the reactor (10);
the reactor (10) is connected with a powder purifying bin (15), and the powder purifying bin (15) is connected with an extrusion granulation system (16);
an online gas chromatograph (17) is arranged in the reactor (10).
2. The method of using the apparatus for producing propylene-butene random copolymerized polypropylene of claim 1, wherein: the method comprises the following steps:
a: propylene in a propylene storage tank (1) firstly enters a solid alkali drying tank (3) to remove free water in the propylene, then enters a propylene degassing tower (4), so that light component gas in the discharge material at the bottom of the propylene degassing tower (4) enters a primary drying tank (5) to further remove moisture in the propylene, then enters a desulfurizing tower (6) to remove sulfur content in the propylene, then sequentially removes arsenic, phosphorus, methylacetylene and propadiene in the propylene through a dearsenization tower (7) and a MAP removal tower (8), finally enters a secondary drying tank (9), and enters a reactor (10) after being dried;
b: liquid butylene in the butylene storage tank (2) directly enters from the bottom of the dryer (11), is discharged from the top, is respectively removed of impurities such as sulfur, water and the like, is filtered by a butylene filter (12) to remove pollutant particles, and then is sent to a circulating gas cooler (13) to enter into the reactor (10);
c: the propylene in the step A and the butylene in the step B react in a reactor (10), a catalyst, an electron donor and a cocatalyst are injected into the reactor (10), materials in the reactor (10) carry out a circulating reaction among the reactor (10), a circulating gas compressor (14) and a circulating gas cooler (13) during the reaction, a product after the reaction enters a powder purifying bin (15), the catalyst which is not completely reacted is removed in the powder purifying bin (15), and then the product and a specific additive enter an extrusion granulation system (16) for granulation.
3. The method for producing propylene-butene random copolymerized polypropylene according to claim 2, wherein: in the step C, the reactor (10) is a single fluidized bed reactor, a catalyst, an electron donor and a cocatalyst are injected into the reactor (10), the catalyst is Consista602, the electron donor is D9600, and the cocatalyst is triethylaluminum;
the condensation capacity of the reactor (10) is controlled to be not less than 6 percent.
4. The method for producing propylene-butene random copolymerized polypropylene according to claim 2, wherein: in the step B, 50kg/h of butylene is slowly added, the adding speed of the butylene is controlled to be 30-40kg/15min, and the dew point temperature difference of the bed is controlled to be less than or equal to 3.0 ℃.
5. The method for producing propylene-butene random copolymerized polypropylene according to claim 2, wherein: in the step C, the hydrogen-carbon mole in the H2/C3 reactor is the mole ratio of hydrogen to propylene monomer, the C4/C3 is the mole ratio of butylene to propylene monomer, and Al/Si is the mole ratio of a cocatalyst, namely triethyl aluminum, to an electron donor D9600;
the calculation of C4/C3 is carried out by taking out the values of the propylene, propane, hydrogen and nitrogen components in the recycle gas by an online gas chromatograph (17) and then adopting an indirect difference method.
6. The method for producing propylene-butene random copolymer polypropylene according to claim 5, wherein: the molar ratio of H2/C3 is 0.014-0.065, the molar ratio of C4/C3 is 0.02-0.06, and the molar ratio of Al/Si is 4-11.
7. The method of the propylene-butene random copolymerized polypropylene production apparatus of the gas phase process according to claim 2, wherein: the storage tanks of the propylene storage tank (1) and the butylene storage tank (2) are made of 304 stainless steel, the design temperature ranges of the propylene storage tank (1) and the butylene storage tank (2) are-196 ℃ to 50 ℃, and the bearing pressure is 0.84 MpaG.
8. The method for producing propylene-butene random copolymerized polypropylene according to claim 2, wherein: the extrusion granulation system (16) adopts an underwater granulation system, the feed pressure is 3-5 Mpa, the temperature of the granulation water is 40-60 ℃, the opening of the throttle valve is 20-40 ℃, the rotating speed of the granulator is 600 plus 1000rpm, and the pressure of the inlet of the melting pump is 1-3 Mpa.
9. The method for producing propylene-butene random copolymerized polypropylene according to claim 2, wherein: in the step C, specific additives in the extrusion granulation system (16) comprise an antioxidant Irganox-1010, an antioxidant Irgafos-168, an acid scavenger, a release agent and a transparent nucleating agent.
10. The method for producing propylene-butene random copolymerized polypropylene according to claim 2, wherein: in the step A, the partial pressure of propylene is gradually reduced to 2.2Mpa at the rate of 0.06Mpa/h, and the temperature of the reactor is gradually reduced to 64 ℃ at the rate of 0.03-0.1 ℃/min.
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