CN216738132U - Metallocene polypropylene raw materials refining plant - Google Patents
Metallocene polypropylene raw materials refining plant Download PDFInfo
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- CN216738132U CN216738132U CN202122923282.0U CN202122923282U CN216738132U CN 216738132 U CN216738132 U CN 216738132U CN 202122923282 U CN202122923282 U CN 202122923282U CN 216738132 U CN216738132 U CN 216738132U
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Abstract
The utility model discloses a metallocene polypropylene raw materials refining plant gets into metallocene polypropylene raw materials refining plant with the coarse propylene that the boundary area comes and carries out purification treatment, metallocene polypropylene raw materials refining plant includes desulfurizing tower, drying tower, dealcoholize tower, dechlorination tower, deoxidation tower in proper order, takes off CO tower, dearsenification tower and takes off CO tower and take off CO2And (4) a tower. The utility model discloses essenceThe tower can be a single tower, a double tower or a plurality of towers, can be connected in parallel or in series, has flexible and changeable design and strong adaptability, can be adjusted according to the composition of raw materials, is not only suitable for refining the metallocene polypropylene raw material, but also can be used for refining the raw material for producing the polypropylene product with ultrahigh cleanliness, and can obtain high-purity refined propylene.
Description
Technical Field
The utility model belongs to petrochemical field macromolecular material, concretely relates to metallocene polypropylene raw materials refining plant.
Background
Polypropylene (PP) is a polymer obtained by polymerizing propylene as a monomer, and is one of the major general plastic products in the world. The reaction equation is as follows:
the polypropylene resin has the advantages of rich raw material sources, balanced mechanical properties, excellent impact resistance, good chemical resistance, transparency, electrical insulation, stress cracking resistance, wear resistance, easy processing and the like, and can be used for a long time at the temperature of 110 ℃. The polypropylene reinforced product has good physical and mechanical properties, can be used as engineering plastic, can be made into injection molding and extrusion products, fibers and films, and can be widely applied to the fields of various industrial and civil plastic products such as automobiles, electric appliances, daily necessities, furniture, packaging, modified engineering plastics and the like.
In 2019, the world production capacity of polypropylene is 1.33 hundred million tons, the production capacity is 1.13 hundred million tons, and the consumption capacity is 1.13 hundred million tons. In 2020, the world production capacity of polypropylene is 1.39 million tons, and the production and consumption are 1.18 million tons, which keeps increasing rapidly. The consumption of Chinese polypropylene is far higher than the average growth level in the world, and the vigorous market demand promotes the explosive growth of the polypropylene capacity. In five general plastics in China, the yield of polypropylene exceeds that of polyethylene and polyvinyl chloride, and the first place is the first place. According to incomplete statistics, 390 ten thousand tons of newly added polypropylene capacity is generated in 2020, and 3241 ten thousand tons of polypropylene capacity is generated in 2020 to the end of 2020. The new production capacity of the polypropylene is estimated to be 659 ten thousand tons in 2021 year, and reaches 3900 ten thousand tons by the end of 2021 year. At present, the production capacity and the supply demand of polypropylene products in China are basically kept level, the requirements on product types and product quality are increased, the product brands produced by domestic polypropylene enterprises are limited, and polypropylene products (such as metallocene polypropylene) in high-end application fields are completely dependent on import.
Metallocene polypropylene is a novel polypropylene product produced by adopting a metallocene polypropylene catalyst, and has the characteristics of narrow relative molecular mass distribution, lower melting point, no generation of soluble short-chain block copolymer and the like. Compared with the traditional Ziegler-Natta (Z-N) catalyst, the metallocene polypropylene catalyst has a single active center, has more accurate regulation and control capability, can be designed, and strictly controls the site of the chain growth process of propylene molecules in the aspects of three-dimensional space and electronic structure. Some polypropylene products, such as syndiotactic polypropylene, are difficult to synthesize with conventional Ziegler-Natta (Z-N) catalysts, which are only available at low temperatures, whereas they can be synthesized with metallocene polypropylene catalysts at normal temperatures. In addition, especially copolymers such as copolymers of propylene with long chain olefins, cycloolefins and diolefins, random and block copolymers of propylene with styrene, and the like, can also be synthesized using metallocene polypropylene catalysts.
Due to the characteristics of the metallocene polypropylene catalyst, the requirement on the quality index of the raw material propylene is very strict, and besides impurities such as water, oxygen, alkyne, carbon monoxide, carbon dioxide, sulfide, arsenide and the like contained in the propylene of a traditional refinery, the existence of trace chlorine impurities in the propylene can also influence the activity and the directional site control capability of the metallocene polypropylene catalyst, even can cause catalyst poisoning to seriously influence the polymerization reaction, and further influence the quality of a product. Thus, metallocene polypropylene catalysts require that some impurities in the feed propylene be removed to ppb (10)-9) At the level of grade, the propylene refining processes of the prior art have not been able to meet the requirements of metallocene polypropylene catalysts.
SUMMERY OF THE UTILITY MODEL
In order to solve the problems and deficiencies of the existing propylene refining technology, the utility model aims to provide a novel refining device for metallocene polypropylene raw materials, which can be applied to the purification of propylene from oil refining, cracking, MTO, PDH and other sources, and can make the propylene meet the use requirements of metallocene polymerization catalysts; can remove H from crude propylene2O、O2、CO、CO2Methanol, acetylene, propine, sulfide, arsenide, chloride and the like, through the refining deviceThe alkene can meet various polymerization requirements of the metallocene polypropylene catalyst.
In order to achieve the above purpose, the utility model discloses there is following technical scheme:
the utility model discloses a metallocene polypropylene raw materials refining plant, metallocene polypropylene raw materials refining plant's refining tower includes desulfurizing tower 1, drying tower 2, dealcoholize tower 3, dechlorination tower 4, deoxidation tower 5 in proper order, takes off CO tower 6, dearsenification tower 7 and takes off CO2A tower 8; crude propylene from a boundary area enters a metallocene polypropylene raw material refining device for treatment; wherein, the crude propylene is connected with the tower bottom feed inlet of a desulfurizing tower 1, the tower top discharge port of the desulfurizing tower 1 is connected with the tower bottom feed inlet of a drying tower 2, the tower top discharge port of the drying tower 2 is connected with the tower bottom feed inlet of a dealcoholization tower 3, the tower top discharge port of the dealcoholization tower 3 is connected with the tower bottom feed inlet of a dechlorination tower 4, the tower top discharge port of the dechlorination tower 4 is connected with the tower bottom feed inlet of a deoxidation tower 5, the tower top discharge port of the deoxidation tower 5 is connected with the tower bottom feed inlet of a CO removing tower 6, the tower top discharge port of the CO removing tower 6 is connected with the tower bottom feed inlet of an arsenic removing tower 7, and the tower top discharge port of the arsenic removing tower 7 is connected with the CO removing tower 72The tower bottom feed inlets of the tower 8 are connected for removing CO2Fine propylene is obtained from a discharge port at the top of the tower 8;
the upper bed layer of the refining tower is sequentially provided with a compaction grid, inert ceramic balls and a wire mesh, and the lower bed layer is sequentially provided with a wire mesh, inert ceramic balls and a support grid; the refining tower catalyst is filled between the upper part wire mesh and the lower part wire mesh;
the dechlorination tower is provided with a separation grid in the middle of an upper bed layer and a lower bed layer besides a compression grid at the upper part and a support grid at the lower part, the upper layer of the dechlorination tower is provided with a W407 sieve for removing inorganic chlorine, and the lower layer is provided with a 5A molecular sieve or a 13X molecular sieve for removing organic chlorine;
the compaction grids, the support grids and the separation grids can play a role in filtering the raw material propylene besides supporting and keeping the catalyst not to be lost;
the inert ceramic ball is used as a supporting and covering material of the catalyst, plays roles of protecting, buffering and filtering the catalyst, and improves the distribution of liquid and gas in the refining tower;
the wire mesh is mainly used for separating the inert ceramic balls from the catalyst and also has the functions of fixing, supporting and filtering.
Wherein, the refining tower can be a single tower, a double tower or a plurality of towers, and can be connected in parallel or in series; the desulfurizing tower 1, the drying tower 2, the dealcoholizing tower 3, the dechlorinating tower 4, the deoxygenating tower 5, the CO removing tower 6, the arsenic removing tower 7 and the CO removing tower2The operation temperature of the tower 8 is 5-50 ℃, and the operation pressure is 1.0-5.0 Mpa.
Wherein, the impurities in the material are orderly removed according to the characteristics of the impurities in the material, and the material is treated by a metallocene polypropylene raw material refining system, wherein H is2O content of less than 10ppb (mol)2Less than 5ppb (mol), less than 5ppb (mol) of CO, CO2Less than 10ppb (mol) NH3Less than 5ppb (mol), less than 10ppb (mol) of acetylene, less than 10ppb (mol) of propine, less than 10ppb (wt) of methanol, less than 5ppb (wt) of total sulfur, less than 3ppb (mol) of COS, and H2The S content is less than 1ppb (mol), the arsenic content is less than 2ppb (wt) and the chlorine content is less than 3ppb (wt).
The utility model discloses a refining method of a metallocene polypropylene raw material refining device, which comprises the following steps:
1) and removing sulfide: crude propylene from a boundary region enters a desulfurizing tower to remove organic sulfur and inorganic sulfur in raw material propylene;
2) deep dehydration: sending propylene from the desulfurizing tower into a drying tower through a liquid propylene pump, and deeply removing water in the raw material propylene;
3) and removing polar compounds: sending propylene from the drying tower into a dealcoholization tower through a liquid propylene pump to remove polar oxygen-containing compounds of alcohol, ether and aldehyde and polar impurities of ammonia and nitrile in the raw material propylene;
4) and removing chloride: sending propylene from the dealcoholization tower into a dechlorination tower through a liquid propylene pump to remove organic chlorine and inorganic chlorine in the raw material propylene;
5) removing alkyne and oxygen: sending propylene from the dechlorination tower into a deoxygenation tower through a liquid propylene pump, and deeply removing trace alkyne and oxygen in the raw material propylene;
6) and removing CO: feeding the propylene from the deoxygenation tower into a CO removal tower through a liquid propylene pump to deeply remove CO in the raw material propylene;
7) and removing arsenide: sending propylene from the CO removal tower into an arsenic removal tower through a liquid propylene pump to remove arsenic and phosphorus impurities in the raw material propylene;
8) and removing CO2: propylene from the dearsenization tower is pumped into the dearsenization CO by a liquid propylene pump2Tower for deep removal of CO generated in the previous purification system2Water and other impurities.
The refining tower can be a single tower, a double tower or a plurality of towers, and can be connected in parallel or in series; the desulfurizing tower 1, the drying tower 2, the dealcoholizing tower 3, the dechlorinating tower 4, the deoxygenating tower 5, the CO removing tower 6, the arsenic removing tower 7 and the CO removing tower2The operation temperature of the tower 8 is 5-50 ℃, and the operation pressure is 1.0-5.0 Mpa;
the desulfurizing tower only uses one W310 fine desulfurizing catalyst, and can remove COS and H in raw materials2Besides S, mercaptan and CS can be effectively removed2The sulfur-containing compound of (1);
the dechlorination tower is provided with an organic chlorine removal unit and an inorganic chlorine removal unit, raw material propylene enters from a lower bed layer, trace organic chlorine is removed through a molecular sieve catalyst (such as a 5A molecular sieve or a 13X molecular sieve) arranged on the lower bed layer, and inorganic chlorine existing or generated in the raw material is removed through a W407 dechlorination agent arranged on an upper bed layer, so that the effective removal of the organic chlorine and the inorganic chlorine can be realized.
The utility model discloses a function of each refining tower of metallocene polypropylene raw materials refining plant is as follows in proper order:
1) removing organic sulfur and inorganic sulfur in the raw materials by using a desulfurizing tower;
2) sending the raw materials into a drying tower to deeply remove water in the raw materials;
3) removing polar oxygen-containing compounds such as alcohol, ether and aldehyde and polar impurities such as ammonia and nitrile in the raw materials by using a dealcoholization tower;
4) the raw materials are sent into a dechlorinating tower to remove organic chlorine and inorganic chlorine in the raw materials;
5) deeply removing trace alkyne and oxygen in the raw material by using a deoxygenation tower;
6) sending the mixture into a CO removal tower to deeply remove CO;
7) removing impurities such as arsenic, phosphorus and the like by using an arsenic removal tower;
8) feeding CO for removing2Tower deep removal of CO produced in front scrubbing system2Water and other impurities.
The technical effects of the utility model:
1. the utility model provides a pair of metallocene polypropylene raw materials refining plant, wherein desulfurizing tower, drying tower, dealcoholize tower, dechlorination tower, deoxidation tower, CO removal tower, dearsenization tower and CO removal2The tower can be a single tower, a double tower or a plurality of towers, can be connected in parallel or in series, has flexible and changeable design, is adjusted according to the composition of raw materials, and can fully play the function of a purifying agent.
2. The conventional raw material propylene desulfurization mechanism comprises a COS removal unit and H2S removal unit, which converts COS into H by using COS hydrolysis catalyst2S, then using another desulfurizing agent to remove H existing or generated in the raw material2And S. The desulfurizing tower only uses a W310 fine desulfurizing catalyst, except COS and H in the raw material which can be removed2Besides S, mercaptan and CS can be effectively removed2And other sulfur-containing compounds.
3. Dechlorination tower be equipped with upper portion bed and lower part bed, propylene gets into by the lower part bed, through the molecular sieve catalyst (like 5A molecular sieve or 13X molecular sieve) desorption trace organochlorine that the lower part bed set up, the inorganic chlorine that exists or produce in the W407 antichlor desorption raw materials that the bed set up of upper portion again realizes organochlorine and inorganic chlorine's effective desorption.
4. The adoption of the refining system of the metallocene polypropylene raw material can remove the content of impurities such as water, oxygen, carbon monoxide, carbon dioxide, alcohols, chlorides, sulfides, arsenide and the like in propylene of a refinery to ppb level (10)-9) Can completely meet the requirements of metallocene catalysts.
5. The utility model has unique process flow design and orderly removes impurities according to the characteristics of the impurities in the materials; the existence of sulfur impurities can affect the activity of a catalyst of a subsequent refining tower, and crude propyleneFirstly, entering a desulfurizing tower for desulfurization; the catalyst of the dealcoholization tower is sensitive to water, and propylene is firstly put into a drying tower for dehydration before entering the dealcoholization tower; chloride in the raw materials has great influence on the catalyst of the deoxygenation tower and should be removed preferentially; the dearsenification tower catalyst has good removal effect on phosphorus and other impurities besides removing arsenic, and is placed behind during process design; CO removal2The tower being placed at the end, except for the deep removal of CO produced in the preceding purification system2Besides, the device can also be used as a protective tower of the whole refining system to deeply remove water and other impurities generated in the previous purification system.
Drawings
FIG. 1 is a process flow diagram of a metallocene polypropylene raw material refining device provided by the present invention;
reference numerals:
1. a desulfurizing tower; 2. a drying tower; 3. a dealcoholization tower; 4. a dechlorination tower; 5. a deoxygenation tower; 6. a CO removal tower; 7. an arsenic removal tower; 8. CO removal2And (4) a tower.
Detailed Description
The invention is described below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
Referring to fig. 1:
the technical scheme of the utility model comprises the following procedures of order refining:
crude propylene from the battery limits is treated in a metallocene polypropylene raw material refining device. Wherein, the crude propylene is connected with the tower bottom feed inlet of a desulfurizing tower 1, the tower top discharge port of the desulfurizing tower 1 is connected with the tower bottom feed inlet of a drying tower 2, the tower top discharge port of the drying tower 2 is connected with the tower bottom feed inlet of a dealcoholization tower 3, the tower top discharge port of the dealcoholization tower 3 is connected with the tower bottom feed inlet of a dechlorination tower 4, the tower top discharge port of the dechlorination tower 4 is connected with the tower bottom feed inlet of a deoxidation tower 5, the tower top discharge port of the deoxidation tower 5 is connected with the tower bottom feed inlet of a CO removing tower 6, the tower top discharge port of the CO removing tower 6 is connected with the tower bottom feed inlet of an arsenic removing tower 7, and the tower top discharge port of the arsenic removing tower 7 is connected with the CO removing tower 72Bottom of column 8The feed inlets are connected for removing CO2And a discharge hole at the top of the tower 8 obtains the refined propylene.
The embodiment is as follows:
TABLE 1 refining column Equipment parameters
TABLE 2
| Serial number | Name(s) | Type of refining column catalyst | Manufacturer of the product |
| 1 | Desulfurizing tower | W310 | Wuhan Kelin Chemical Industry Group Co.,Ltd. |
| 2 | Drying tower | HTMS-3A molecular sieve | Liaoning Haitai science and technology development Limited |
| 3 | Dealcoholization tower | RM-1 dealcoholizing agent | Liaoning Haitai science and technology development Limited |
| 4 | Dechlorination tower | 5A molecular sieve and 13X molecular sieve | Henan Mingze environmental protection science and technology Co., Ltd |
| W407 | Wuhan Kelin Chemical Industry Group Co.,Ltd. | ||
| 5 | Deoxygenation tower | SRO-1 | Beijing environmental protection Trimerism Co Ltd |
| 6 | CO removing tower | COR-1 | Liaoning Haitai science and technology development Co., Ltd |
| 7 | Dearsenication tower | STAS-2 | Beijing environmental protection Trimerism Co Ltd |
| 8 | CO-removing 2 tower | RCD-1 | Liaoning Haitai science and technology development Limited |
This example is applied to a metallocene polypropylene raw material purification apparatus for SPG process with a propylene throughput of 15 ten thousand tons/year (18.75t/h), and the specific equipment parameters are shown in Table 1. The processing steps of the refining device for the raw material propylene in the embodiment comprise the following steps:
1. removing sulfides: crude propylene from a boundary region enters a desulfurizing tower to remove organic sulfur and inorganic sulfur in raw material propylene;
2. deep dehydration: sending propylene from the desulfurizing tower into a drying tower through a liquid propylene pump, and deeply removing water in the raw material propylene;
3. removing polar compounds: sending propylene from the drying tower into a dealcoholization tower through a liquid propylene pump to remove polar oxygen-containing compounds such as alcohol, ether and aldehyde and polar impurities such as ammonia and nitrile in the raw material propylene;
4. removing chloride: sending propylene from the dealcoholization tower into a dechlorination tower through a liquid propylene pump to remove organic chlorine and inorganic chlorine in the raw material propylene;
5. removing alkyne and oxygen: sending propylene from the dechlorination tower into a deoxygenation tower through a liquid propylene pump, and deeply removing trace alkyne and oxygen in the raw material propylene;
6. removing CO: feeding the propylene from the deoxygenation tower into a CO removal tower through a liquid propylene pump to deeply remove CO in the raw material propylene;
7. removing arsenide: sending propylene from the CO removal tower into an arsenic removal tower through a liquid propylene pump to remove impurities such as arsenic, phosphorus and the like in the raw material propylene;
8. CO removal2: propylene from the dearsenization tower is pumped into the dearsenization CO by a liquid propylene pump2Tower for deep removal of CO generated in the previous purification system2Water and other impurities.
This example summarizes the catalysts used in the different finishing columns as shown in table 2. Table 3 shows the outlet propylene component of the propylene stripper of this example. Table 4 is the impurity content of this embodiment strip tower export propylene after through the utility model discloses metallocene polypropylene raw materials refining plant purification treatment.
TABLE 3
TABLE 4
| Components | Unit of measurement | Composition of |
| Acetylene | ppb，mol | ≤10.0 |
| Propyne | ppb，mol | ≤10.0 |
| CO | ppb，mol | ≤5.0 |
| CO2 | ppb，mol | ≤10.0 |
| Oxygen gas | ppb，mol | ≤5.0 |
| Water (W) | ppb，wt | ≤10.0 |
| Total sulfur | ppb，wt | ≤5.0 |
| H2S | ppb，mol | ≤1.0 |
| COS | ppb，mol | ≤3.0 |
| NH3 | ppb，mol | ≤5.0 |
| Arsenic hydride | ppb，wt | ≤2.0 |
| Methanol | ppb，wt | ≤10 |
| Chloride compound | ppb，wt | ≤3.0 |
The utility model discloses a metallocene polypropylene raw materials refining plant, the process flow design is unique, and the regeneration energy consumption is low, and catalyst long service life can obtain the fine propylene of high purity, can satisfy the index requirement of metallocene catalyst to raw materials propylene.
Refined tower can be single tower, two towers or multitower, can connect in parallel and also can establish ties, and the design is nimble changeable, and strong adaptability can constitute the adjustment according to the raw materials, not only adapts to the metallocene polypropylene raw materials and refines, also can be used to the raw materials of super high cleanliness factor polypropylene product production to refine, can obtain the fine propylene of high purity, can satisfy the index requirement of metallocene polypropylene catalyst to raw materials propylene.
As described above, the present invention can be realized more fully. The above is only the comparatively reasonable embodiment of the present invention, the protection scope of the present invention includes but is not limited thereto, and any person skilled in the art based on the technical solution of the present invention includes the insubstantial variability changes within the scope of the present invention.
Claims (3)
1. A metallocene polypropylene raw material refining device is characterized in that: the refining tower of the metallocene polypropylene raw material refining device sequentially comprises a desulfurizing tower (1), a drying tower (2), a dealcoholizing tower (3), a dechlorinating tower (4), a deoxidizing tower (5), a CO removing tower (6), an arsenic removing tower (7) and CO removing2A tower (8); crude propylene from a boundary area enters a metallocene polypropylene raw material refining device for treatment; wherein, the crude propylene is connected with a tower bottom feed inlet of a desulfurizing tower (1), a tower top discharge port of the desulfurizing tower (1) is connected with a tower bottom feed inlet of a drying tower (2), a tower top discharge port of the drying tower (2) is connected with a tower bottom feed inlet of a dealcoholization tower (3), a tower top discharge port of the dealcoholization tower (3) is connected with a tower bottom feed inlet of a dechlorination tower (4), a tower top discharge port of the dechlorination tower (4) is connected with a tower bottom feed inlet of a deoxidation tower (5), a tower top discharge port of the deoxidation tower (5) is connected with a tower bottom feed inlet of a CO removing tower (6), a tower top discharge port of the CO removing tower (6) is connected with a tower bottom feed inlet of a dearsenization tower (7), and a tower top discharge port of the dearsenization tower (7) is connected with a tower bottom feed inlet of the CO removing tower (6)2The tower bottom feed inlets of the tower (8) are connected for removing CO2A discharge hole at the top of the tower (8) obtains fine propylene;
the upper bed layer of the refining tower is sequentially provided with a compaction grid, inert ceramic balls and a wire mesh, and the lower bed layer is sequentially provided with a wire mesh, inert ceramic balls and a support grid; the refining tower catalyst is filled between the upper part wire mesh and the lower part wire mesh;
the dechlorination tower is provided with a separation grid in the middle of an upper bed layer and a lower bed layer besides a compression grid at the upper part and a support grid at the lower part, the upper layer of the dechlorination tower is provided with a W407 sieve for removing inorganic chlorine, and the lower layer is provided with a 5A molecular sieve or a 13X molecular sieve for removing organic chlorine;
the compaction grids, the support grids and the separation grids can play a role in filtering the raw material propylene besides supporting and keeping the catalyst not to be lost;
the inert ceramic ball is used as a supporting and covering material of the catalyst, plays roles of protecting, buffering and filtering the catalyst, and improves the distribution of liquid and gas in the refining tower;
the wire mesh is mainly used for separating the inert ceramic balls from the catalyst and also has the functions of fixing, supporting and filtering.
2. The apparatus for refining a metallocene polypropylene raw material according to claim 1, characterized in that: the refining tower is configured into a single tower, a double tower or a plurality of towers, and can be connected in parallel or in series.
3. The apparatus for refining a metallocene polypropylene raw material according to claim 1, characterized in that: the device comprises a desulfurizing tower (1), a drying tower (2), a dealcoholizing tower (3), a dechlorinating tower (4), a deoxidizing tower (5), a CO removing tower (6), an arsenic removing tower (7) and CO removing2The operation temperature of the tower (8) is 5-50 ℃, and the operation pressure is 1.0-5.0 Mpa.
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