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CN114956939B - Ethylene oligomerization regulation and control method - Google Patents

Ethylene oligomerization regulation and control method Download PDF

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Publication number
CN114956939B
CN114956939B CN202210773304.6A CN202210773304A CN114956939B CN 114956939 B CN114956939 B CN 114956939B CN 202210773304 A CN202210773304 A CN 202210773304A CN 114956939 B CN114956939 B CN 114956939B
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temperature
pnp
reaction
diphenylphosphino
bis
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CN114956939A (en
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丁明强
王金强
陈冠良
王大林
车传亮
张彦雨
王磊
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a control process for ethylene oligomerization, in particular to a method for maintaining reaction selectivity and byproduct polymer in a control range under a state of large fluctuation of reaction temperature. The oligomerization process with ideal selectivity and byproduct polymer content is realized on the premise of not changing the main oligomerization formula by controlling the reaction temperature and time of the system cooperatively so that the two satisfy a specific time-temperature equivalent relationship.

Description

Ethylene oligomerization regulation and control method
Technical Field
The invention belongs to the field of olefin polymerization, and in particular relates to a method for reducing PE (polyethylene) as a byproduct of ethylene oligomerization reaction on the basis of not sacrificing the selectivity and polymerization activity of a product.
Background
The linear alpha-olefin has wide industrial application, and the oligomer thereof can be used in various fields such as plasticizers, fatty acids, lubricating oil additives and the like; the copolymer can be used for producing polyolefin elastomer, and is used in various fields of shoe materials, polymer modification, automobiles and the like.
The production process of the linear alpha-olefin mainly comprises selective oligomerization and non-selective oligomerization, the traditional non-selective oligomerization often obtains multi-component linear alpha-olefin which is in normal distribution characteristics, single components or several mixed components are separated according to the needs in industry for use, the separation process is complex, and the proportion of target products (1-hexene and/or 1-octene) is difficult to regulate and control; while ethylene high-selectivity catalysis generates single linear alpha-olefin with specific carbon number, which is originally reported by Sasol corporation (CN 100548946C), adopts chromium compound with nitrogen-phosphorus coordination skeleton as catalyst, catalyzes ethylene tetramerization at 45 ℃ and 4.5MPa to generate 1-hexene of 16.6-32.7%, and 1-octene of 44-67%.
The catalyst is a low-temperature catalyst due to the specificity of the Cr/PNP catalyst system containing oligomerization, and the selectivity of the reaction is sacrificed and the byproduct polymer is greatly increased, even the catalyst is deactivated due to the too high temperature. The ethylene oligomerization reaction has larger heat release amount (heat insulation temperature rise 136K) and faster heat release rate, and in actual production, the polymer is difficult to control in a stable range all the time due to the influence of accumulation of the polymer on heat transfer and mass transfer, so that the pre-judgment of proper operation time is very important.
Disclosure of Invention
The invention aims to provide a method for reducing the byproduct polymer of ethylene oligomerization, which can reduce the content of PE byproduct of ethylene oligomerization on the basis of not sacrificing the selectivity and polymerization activity of the product.
The inventor surprisingly found that in the existing catalytic system, the relationship between the reaction temperature and the reaction time is skillfully established, the residence time is controlled according to the reaction temperature, the advantages of the conversion rate, the activity and the selectivity of the reaction can be fully exerted, and the system byproduct polymer can be controlled in an ideal range.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a regulation and control method for oligomerization of ethylene, the process is that under a certain pressure, the temperature and time are maintained to meet the following defined relation, so that ethylene is subjected to selective oligomerization reaction in a system comprising a chromium tetrahydrofuran trichloride catalyst/PNP ligand, aluminum alkyl and an organic solvent to generate alpha-olefin;
wherein T is n And T n+1 A certain specific temperature and the next temperature which is raised due to an abnormality, respectively; t is t n And t n+1 Respectively corresponding to a specific temperature T n And T n+1 Lower residence time.
In the present invention, when T 0 At=40 ℃, t 0 Less than or equal to 120min; when T is 1 At the time of =50deg.C,when T is 2 At =60 ℃, t 2 Less than or equal to 120/emin; when T is 3 When=70 ℃, the%>When T is 4 At=80 ℃, t 4 ≤120/e 2 min。
In the invention, the reaction pressure is controlled to be 4.0-5.0 MPaG, the reaction temperature T is controlled to be 40-80 ℃, and the reaction time T is controlled to be 10-120min.
In the invention, the concentration of the tetrahydrofuran chromium trichloride catalyst is 0.5-10umol/L.
In the invention, the PNP ligand is a compound with a skeleton of a phosphine-nitrogen-phosphine structure, and is selected from one or more of N, N-bis (diphenylphosphino) -isopropylamine (iPr-PNP), N-bis (diphenylphosphino) -tert-butylamine (tBu-PNP), N-bis (diphenylphosphino) -1, 2-dimethylpropylamine (1, 2-DMP-PNP) and N, N-bis (diphenylphosphino) -cyclohexylamine (Cy-PNP).
In the present invention, the molar ratio of the tetrahydrofuran-containing chromium trichloride catalyst to its corresponding ligand is from 0.5 to 5, preferably from 1 to 2.
In the invention, the alkyl aluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO), and is preferably used by compounding the alkyl aluminum and the alkyl aluminoxane.
In the present invention, the molar ratio of the alkyl aluminum compound to the chromium-containing catalyst is selected to be 100 to 1000, preferably 200 to 500.
In the invention, the organic solvent is selected from one or more of n-hexane, n-heptane, cyclohexane, methylcyclohexane, tetrahydrofuran, toluene or xylene.
In the invention, the content of 1-hexene and 1-octene in the alpha-olefin reaches 88 to 91 percent, and the content of the byproduct polymer PE is less than 0.3 weight percent.
It is known that ethylene oligomerization is a strongly exothermic reaction, and that the catalyst system is of a type that is not resistant to high temperatures, plus the production of by-product polymers at the target reaction temperature. The byproduct polymer can adhere to the inner walls of the reaction kettle and the heat exchanger and is entangled on the stirrer, so that heat transfer and mass transfer are affected, the later temperature of the reaction system greatly fluctuates, the selectivity of the main reaction is sacrificed, and the amount of the byproduct polymer is further deteriorated. The invention aims to alleviate the abnormal state to a certain extent by controlling the reaction residence time on the premise that the temperature cannot be regulated and controlled in a short period.
Compared with the prior art, the invention has the beneficial effects that:
(1) On the one hand, the invention provides a simple and efficient process for regulating and controlling the reaction selectivity and the polymer on the premise of not changing the main formula of the reaction system, and avoids complex and expensive catalyst design and synthesis.
(2) On the other hand, the invention uses the 'class time-temperature equivalent relationship' under the condition of larger fluctuation of the reaction temperature or approaching to the runaway, maintains the selectivity of the reaction and the generation of byproduct PE by adjusting the reaction residence time, avoids the occurrence of large fluctuation of product indexes, and provides additional operation time for production personnel.
Detailed Description
The following examples further illustrate the technical solutions provided by the present invention, but the present invention is not limited to the listed examples, but includes any other known modifications within the scope of the claims.
1. The raw material information related to the invention is as follows:
TABLE 1 sources of raw materials and specifications thereof
Name of the name Specification of specification Source
Tetrahydrofuran chromium trichloride 98％ Shandong Seiya chemical Co., ltd
N, N-bis (diphenylphosphino) -isopropylamine 98％ SINOCOMPOUND CATALYSTS Co.,Ltd.
N, N-bis (diphenylphosphino) -tert-butylamine 98％ SINOCOMPOUND CATALYSTS Co.,Ltd.
N, N-bis (diphenylphosphino) -1, 2-dimethylpropylamine 98％ Sorvy fine chemical Co Ltd
N, N-bis (diphenylphosphino) -cyclohexylamine 98％ Sorvy fine chemical Co Ltd
Methylcyclohexane (MCH) AR Ara Ding Shenghua technologies Co Ltd
Trimethylaluminum (TMA) 1.0mol/L Beijing Enoka technology Co.Ltd
Triisobutylaluminum (TIBA) 1.0mol/L Beijing Enoka technology Co.Ltd
Modified methylaluminoxane (MMAO-3A) 7% solution Akzo Nobel Co
2-ethyl-1-hexanol 99％ Ara Ding Shenghua technologies Co Ltd
2. The test method of the sample in the invention is as follows:
the liquid phase products are characterized by gas chromatography, so that the quality of each liquid phase product is obtained, and the solid products are separated, dried and weighed;
analysis conditions for gas chromatography: the temperature of the sample injection product is 250 ℃; the temperature of the column box is 35 ℃;
heating program: firstly, keeping at 35 ℃ for 10 minutes, then raising the temperature to 250 ℃ at the speed of 10 ℃/min, then keeping at 250 ℃ for 10 minutes, and then starting to cool until the temperature reaches the room temperature;
detector temperature: 250 ℃; and (3) a carrier: 1.0Mpa; air: 0.03Mpa; hydrogen gas: 0.03Mpa;
characterization of the product with n-nonane as an internal standard, the calculation method is as follows:
wherein m1 represents the mass of a certain substance, m is the mass of nonane, a1 is the peak area of the substance measured in GC, and a is the peak area of n-nonane measured in GC. k is a correction coefficient.
Example 1
A4L high pressure stainless steel reactor (with side discharge line, overflow port position 2.0L) was heated to 120deg.C, evacuated for 3h, during which time nitrogen was replaced three times, then evacuated and replaced three times with hydrogen. Cooling to room temperature, introducing hydrogen at 0.5Mpa, injecting 1945mL of dehydrated and deoxidized methylcyclohexane, 16.0mL of trimethylaluminum, 23.0mL of MMAO-3A and 16.0mL of pre-prepared PNP ligand (N, N-bis (diphenylphosphino) -tert-butylamine/chromium trichloride catalyst solution with molar concentration of 1.0umol/mL (molar ratio of 1.2:1) into the reactor by a plunger pump, maintaining ethylene at 4.5MPa and under the conditions of initial temperature of 40 ℃ and rotating speed of 800rpm, continuously introducing solvent MCH, main catalyst and cocatalyst into the reactor by a high-pressure solvent plunger pump under the conditions of maintaining system main catalyst (Cr/PNP) concentration solution at 8umol/L, al/Cr ratio=400 and residence time of 120min, laterally introducing a buffer tank containing excessive quenching agent 2-ethyl-1-hexanol into the side line, continuously discharging the reaction liquid phase product, taking 100mL of the reaction liquid after termination, carrying out suction filtration, carrying out GC at the condition of 100mL, carrying out vacuum filtration, and weighing, carrying out analysis on the solid activity in the oven at 80 ℃ and weighing, and carrying out the analysis on the solid activity in the oven at 12 h.
Example 2
The remaining operations of example 1 were repeated except that the starting temperature was increased to 50℃and the dwell time was adjusted to 72 min.
Example 3
The remaining operations of example 1 were repeated except that the starting temperature was increased to 60℃and the dwell time was adjusted to 44 min.
Example 4
The remaining operations of example 1 were repeated except that the starting temperature was increased to 70℃and the dwell time was adjusted to 26 min.
Example 5
The remaining operations of example 1 were repeated except that the starting temperature was increased to 80℃and the dwell time was adjusted to 16 min.
Example 6
A4L high pressure stainless steel reactor (with side discharge line, overflow port position 2.0L) was heated to 120deg.C, evacuated for 3h, during which time nitrogen was replaced three times, then evacuated and replaced three times with hydrogen. Cooling to room temperature, introducing hydrogen at 0.5Mpa, injecting 1940mL of dehydrated and deoxidized methylcyclohexane, 20.0mL of triisobutylaluminum, 20.0mL of MMAO-3A and 20.0mL of pre-prepared PNP ligand (N, N-bis (diphenylphosphino) -isopropylamine/chromium trichloride catalyst solution with molar concentration of 1.0umol/mL (molar ratio of 1.2:1) into the reaction kettle by a plunger pump, maintaining ethylene at 4.5MPa and under the conditions of initial temperature of 50 ℃ and rotating speed of 800rpm, after obvious temperature rise, continuously introducing solvent MCH, main catalyst and cocatalyst into the reaction kettle by a high-pressure solvent plunger pump under the conditions of maintaining system main catalyst (Cr/PNP) concentration solution at 10umol/L, al/Cr ratio=300 and residence time of 72min, introducing a product buffer tank with excessive quenching agent of 2-ethyl-1-hexanol into a side line, continuously discharging the liquid phase product, taking 100mL of the reaction liquid after the reaction is stopped, carrying out GC at the initial temperature of 50 ℃ and carrying out GC at the temperature of 80 ℃ and carrying out the analysis of the activity of solid product in an oven under the conditions of 12 h.
Example 7
A4L high pressure stainless steel reactor (with side discharge line, overflow port position 2.0L) was heated to 120deg.C, evacuated for 3h, during which time nitrogen was replaced three times, then evacuated and replaced three times with hydrogen. Cooling to room temperature, introducing hydrogen at 0.5Mpa, injecting 1976mL of dehydrated and deoxidized methylcyclohexane, 6.0mL of triethylaluminum, 12mL of MMAO-3A and 6mL of pre-prepared PNP ligand (N, N-bis (diphenylphosphino) -1, 2-dimethylpropylamine/chromium tetrahydrofuran trichloride catalyst solution (molar ratio 1.2:1) with molar concentration of 1.0umol/mL into the reaction kettle by a plunger pump, maintaining ethylene at 4.5MPa and under the conditions of initial temperature 60 ℃ and rotating speed of 800rpm, after obvious temperature rise occurs, continuously introducing solvent MCH, main catalyst and cocatalyst into the reaction kettle by a high-pressure solvent plunger pump under the conditions of maintaining system main catalyst (Cr/PNP) concentration solution at 3umol/L, al/Cr ratio=300 and residence time of 44min, laterally introducing a product buffer tank containing excessive quenching agent 2-ethyl-1-hexanol into the side line, continuously discharging the liquid phase product, taking 100mL of the reaction liquid after reaction is stopped, carrying out GC at the initial temperature of 60 ℃ and carrying out GC at the temperature of 80 ℃ and carrying out vacuum analysis on the activity of solid products in the oven at the conditions of 80 h.
Comparative example 1
The remaining procedure of example 1 was repeated except that chromium tetrahydrofuran trichloride was replaced with chromium acetylacetonate.
Comparative example 2
The remaining operation of example 1 was repeated except that the concentration of chromium trichloride in tetrahydrofuran was changed to 12 umol/L.
Comparative example 3
The remaining operation of example 2 was repeated except that the residence time of the system was adjusted to 80 min.
Comparative example 4
The remaining operation of example 4 was repeated except that the residence time of the system was adjusted to 30 min.
Comparative example 5
The remaining operation of example 5 was repeated except that the residence time of the system was adjusted to 20min.
The composition of the oligomerization reaction obtained by each of the methods shown above is shown in the following table:
operational examples Temperature regulation/°c Time adjustment/min Conversion/% 1-C6/％ 1-C8/％ PE/％
Example 1 0 Without any means for 85 41.2 49.7 0.21
Example 2 Rise 10 Down to 72 83 41.4 49.6 0.24
Example 3 Elevation 20 Down to 44 84 41.7 49.3 0.27
Example 4 Elevation 30 Down to 26 81 41.9 58.3 0.28
Example 5 Elevation 40 Down to 16 82 42.8 47.5 0.3
Example 6 Rise 10 Down to 72 89 23.7 63.6 0.23
Example 7 Elevation 20 Down to 44 73 32.3 54.2 0.33
Comparative example 1 0 Without any means for 58 40.2 46.7 0.43
Comparative example 2 0 Without any means for 85 41.7 46.9 0.52
Comparative example 3 Elevation 20 Up to 80 82 32.8 56.1 0.41
Comparative example 4 Elevation 30 Up to 30 80 42.5 45.7 0.64
Comparative example 5 Elevation 40 Up to 20 80 34.8 53.1 0.73
From the examples it can be seen that: by adopting the empirical formula provided by the invention, abnormal effects brought by partial temperature can be counteracted by smartly adjusting the residence time of the reaction when the temperature is abnormal or the fluctuation is large, for example, if the operation period is proper, the fluctuation of the total selectivity, the polymer content and the conversion rate of the reaction is not large; in the comparative example, if the reaction time is not properly adjusted or the kind/concentration of the chromium-containing catalyst is not properly adjusted, the increase of the by-product polymer is more remarkable, and it is expected that if the time is too short, the conversion is not satisfactory, resulting in the sacrifice of production cost and efficiency, and the higher the temperature abnormality is, the higher the sensitivity of the effect is. Therefore, the invention provides a new idea for reducing production fluctuation and improving the operation period of equipment technicians by adjusting the relation between abnormal temperature rise and residence time in the reaction process to realize effective balance of reaction conversion rate, overall selectivity and byproduct PE.
In summary, the foregoing is merely representative examples of the present invention and is merely illustrative of the present invention and not intended to limit the present invention, and any modifications of the present invention, including equivalent substitutions and additions of various materials, conversion of continuous or batch processes, etc., are included in the scope of the present invention, as will be appreciated by those skilled in the art. The scope of the invention is defined by the claims.

Claims (9)

1. A regulation and control method for ethylene oligomerization is characterized in that the method is characterized in that under a certain pressure, the temperature and time are maintained to meet the following defined relation, so that ethylene is subjected to selective oligomerization in a system comprising a chromium tetrahydrofuran trichloride catalyst/PNP ligand, an aluminum alkyl compound and an organic solvent to generate alpha-olefin;
wherein T is n And T n+1 A certain specific temperature and the next temperature which is raised due to an abnormality, respectively; t is t n And t n+1 Respectively corresponding to a specific temperature T n And T n+1 Lower residence time.
2. The method of claim 1, wherein T is 0 At=40 ℃, t 0 Less than or equal to 120min; the reaction pressure is controlled to be 4.0-5.0 MPaG, the reaction temperature T is controlled to be 40-80 ℃, and the reaction time T is controlled to be 10-120min.
3. The method of claim 1, wherein the concentration of the chromium tetrahydrofuran trichloride catalyst is from 0.5 to 10umol/L.
4. A method according to any one of claims 1 to 3, wherein the PNP ligand is a compound having a phosphazene structure as a backbone and is selected from one or more of N, N-bis (diphenylphosphino) -isopropylamine (iPr-PNP), N-bis (diphenylphosphino) -tert-butylamine (tBu-PNP), N-bis (diphenylphosphino) -1, 2-dimethylpropylamine (1, 2-DMP-PNP), N-bis (diphenylphosphino) -cyclohexylamine (Cy-PNP).
5. A process according to any one of claims 1 to 3, wherein the molar ratio of the tetrahydrofuran-containing chromium trichloride catalyst to its corresponding ligand is from 0.5 to 5.
6. A method according to any one of claims 1 to 3, wherein the alkyl aluminium compound is selected from one or more of trimethylaluminium, triethylaluminium, triisobutylaluminium, trioctylaluminium, methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO).
7. A process according to any one of claims 1 to 3, wherein the molar ratio of the alkyl aluminium compound to the chromium-containing catalyst is selected to be in the range 100 to 1000.
8. A method according to any one of claims 1 to 3, wherein the organic solvent is selected from one or more of n-hexane, n-heptane, cyclohexane, methylcyclohexane, tetrahydrofuran, toluene or xylene.
9. A process according to any one of claims 1 to 3, wherein the alpha-olefin has a 1-hexene and 1-octene content of 88 to 90% and the by-product polymer PE content is less than 0.3% by weight.
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