CN116072240B - Method for confirming mole percentage and in-situ quantity of various monomers in gas phase and liquid phase in solution method olefin polymerization reaction system - Google Patents
Method for confirming mole percentage and in-situ quantity of various monomers in gas phase and liquid phase in solution method olefin polymerization reaction system Download PDFInfo
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 27
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The invention provides a method for confirming the mole percentage and the placement amount of various monomers in a gas phase and a liquid phase in a solution-method olefin polymerization reaction system in real time. The method comprises the following steps: obtaining the mole percent of each monomer in the gas phase, and further obtaining the mole percent of each monomer in the liquid phase; obtaining the placed amount of each monomer in the gas phase according to the mole percent of each monomer in the gas phase; obtaining the placed amount of each monomer in the liquid phase according to the mole percent of each monomer in the liquid phase; the amount of each monomer in the polymerization reaction system and the total amount of monomer in the polymerization reaction system are obtained according to the amount of each monomer in the gas phase and the amount of each monomer in the liquid phase. The method can accurately determine the concentration and the in-situ quantity of each monomer in the polymerization reaction system, can accurately regulate the flow of a molecular weight regulator and the like by controlling the parameters, realizes the automatic regulation of the molecular weight of a product, and ensures the stability of the quality of the product.
Description
Technical Field
The invention relates to a method for confirming the mole percentage and the in-situ quantity of various monomers in gas phase and liquid phase in a solution-method olefin polymerization reaction system in real time, belonging to the technical field of olefin polymerization.
Background
The solution process olefin polymerization technology uses Ziegler-Natta type catalyst system, uses C5-C8 straight chain alkane as solvent, uses ethylene, propylene and so on as polymerization monomer, and can produce homopolymers or copolymers of polyethylene, polypropylene and so on.
Taking ethylene propylene rubber production as an example, ethylene propylene rubber is an olefin copolymer, and polymerization reaction is the most important technological process of an ethylene propylene rubber production device. In the polymerization reaction unit, the ethylene, propylene, a third comonomer (ENB or DCPD) and a solvent are added into a polymerization reactor together, and copolymerization reaction is carried out under the initiation of a catalyst to generate a high molecular polymer-ethylene propylene rubber, and various monomers, the catalyst and the generated polymer are dissolved in the solvent.
The polymerization reaction monomers, catalyst and solvent are metered and then continuously added into the reactor, the temperature, pressure, liquid level and gas flow rate discharged from the reactor are controlled, the polymerization reaction heat causes a part of monomers and solvent to evaporate from the reactor, and the evaporated gas is compressed and condensed and then returned to the reactor. After the polymerization reaction is completed in the reactor, the monomer enters a monomer separation tower, unreacted monomer is distilled out, and the distilled monomer is returned to the reactor for recycling. The method can keep the stability of working conditions and master the concentration and the amount of various monomers in gas phase and liquid phase in a polymerization reaction system in real time, and is very important for controlling the quality of products. But there is currently no real-time confirmation method for the concentration and the amount of each monomer in the liquid phase.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a method for confirming the concentration and the amount of each monomer in a liquid phase in real time, wherein the polymerization amount, the concentration of a polymer at an important control point and the amount of each monomer (including main inert substances) in a polymerization reaction system can be obtained by processing measurable technological parameters in the polymerization reaction process and calculating.
In order to achieve the above object, the present invention provides a method for real-time confirmation of mole percentages and in-situ amounts of various monomers in gas and liquid phases in a solution-process olefin polymerization reaction system, comprising the steps of:
(1) Obtaining the mole percent of each monomer in the gas phase;
(2) Obtaining the mole percent of each monomer in the liquid phase according to the mole percent of each monomer in the gas phase, wherein the mole percent of each monomer in the liquid phase = the mole percent of each monomer in the gas phase ≡the gas-liquid equilibrium coefficient of each monomer;
(3) Obtaining the placed amount of each monomer in the gas phase according to the mole percent of each monomer in the gas phase, wherein the placed amount of each monomer in the gas phase = the gas phase volume of the reactor x the mole percent of each monomer in the gas phase x the temperature pressure compensation coefficient x the mole mass of the corresponding monomer ≡22.4;
(4) Obtaining the in-place amount of each monomer in the liquid phase according to the mole percent of each monomer in the liquid phase, wherein the in-place amount of each monomer in the liquid phase = the liquid phase working volume of the reactor x the liquid phase density x the mole mass of each monomer x the mole percent of each monomer in the liquid phase ≡total component mole fraction weighted molecular weight in the liquid phase;
(5) The amount of each monomer in the polymerization reaction system and the total amount of monomer in the polymerization reaction system are obtained according to the amount of each monomer in the gas phase and the amount of each monomer in the liquid phase.
According to a specific embodiment of the present invention, preferably, the solution process olefin polymerization reaction system refers to a liquid phase and a gas phase in which a reaction monomer is reacted in a reactor, and in which the reaction monomer, a solvent, a reaction product, and some inert substances are present.
According to a particular embodiment of the invention, preferably, in step (1), the mole percentage of the monomer in the gas phase is obtained by gas chromatography.
According to a specific embodiment of the present invention, preferably, in step (3), the temperature pressure compensation coefficient is obtained by the following formula:
temperature-pressure compensation coefficient= (a×273)/(1.033× (polymerization temperature value +273));
Wherein a = polymerization pressure value/98.0665+1.033, wherein the polymerization pressure value is in kPa and a is in atm, the above process is actually a conversion of pressure units of kPa/atm; the polymerization temperature values are in units of ℃.
According to a specific embodiment of the present invention, preferably, in step (4), the total component mole fraction weighted molecular weight in the liquid phase is the sum of the product of the molar mass of each component and the mole percent of each component, the components comprising monomer, inert and solvent.
According to a specific embodiment of the present invention, preferably, in step (5), the amount of each monomer present in the polymerization reaction system is obtained by the following formula:
the amount of each monomer in the polymerization reaction system = the amount of the monomer in the gas phase + the amount of the monomer in the liquid phase;
the total monomer placement amount of the polymerization reaction system is the sum of the placement amounts of the monomers in the polymerization reaction system.
The method provided by the invention is suitable for the olefin homo-polymerization or copolymerization process by a solution method.
According to a specific embodiment of the present invention, preferably, the solution process olefin polymerization reaction system is an olefin polymerization system using ethylene and propylene as raw materials and hexane as a solvent, and the real-time confirmation method comprises:
(1) Obtaining a mole percentage ATc of ethylene in the gas phase, a mole percentage ATc of propylene in the gas phase, and a mole percentage ATc of propane in the gas phase;
(2) Obtaining the mole percent of ethylene, propylene, propane in the liquid phase according to the mole percent of ethylene, propylene, propane (inert substance) in the gas phase, wherein:
X ethylene =ATc2÷K Ethylene ；
X Propylene =ATc3÷K Propylene ；
X Propane = ATc30÷K Propane ；
Wherein X is Ethylene 、X Propylene 、X Propane Represents the mole percent of ethylene, propylene and propane in the liquid phase, and the unit is mol%;
K ethylene 、K Propylene 、K Propane Respectively representing the vapor-liquid equilibrium coefficients of ethylene, propylene and propane;
(3) Obtaining the in-situ amount of ethylene, propylene and propane in the gas phase according to the mole percent of the ethylene, propylene and propane in the gas phase, wherein:
ethylene in the gas phase in the quantity=v Air flow ×ATc2÷100×PT×28÷22.4；
Propylene in gas phase in quantity=v Air flow ×ATc3÷100×PT×42÷22.4；
Propane in gas phase in quantity=v Air flow ×ATc3÷100×PT×44÷22.4；
Wherein:
the unit of the amount of ethylene, propylene and propane in the gas phase is kg;
V air flow Representing the volume of the gas phase in the reactor, in m 3 ；
PT is a temperature-pressure compensation coefficient, pt= (a×273)/(1.033× (b+273));
a=polymerization pressure value/98.0665+1.033, wherein the polymerization pressure value is in units of kPa; b is a polymerization temperature value of +230, and the unit of the polymerization temperature value is DEG C;
(4) Obtaining the in-situ amount of ethylene, propylene and propane in the liquid phase according to the mole percent of the ethylene, propylene and propane in the liquid phase, wherein:
ethylene in liquid phase in quantity = V Liquid and its preparation method ×ρ Liquid and its preparation method ×28×W；
Propylene in liquid phase in quantity=v Liquid and its preparation method ×ρ Liquid and its preparation method ×42×W；
Propane in liquid phase in quantity = V Liquid and its preparation method ×ρ Liquid and its preparation method ×44×W；
Wherein:
the unit of the amount of ethylene, propylene and propane in the liquid phase is ton;
V liquid and its preparation method Is the working volume of the liquid phase in the reactor, the unit is m 3 ；
ρ Liquid and its preparation method Is the density of liquid phase, and the unit is ton/m 3 ；
W is the molar fraction weighted molecular weight of the total components in the liquid phase;
(5) Obtaining the in-situ amount of ethylene, propylene and propane in the polymerization reaction system and the total monomer in the polymerization reaction system according to the in-situ amount of ethylene, propylene and propane in the gas phase and the in-situ amount of ethylene, propylene and propane in the liquid phase, wherein:
ethylene in the polymerization system = ethylene in the gas phase +.1000+ ethylene in the liquid phase;
propylene in the polymerization system = propylene in the gas phase/(1000 + propylene in the liquid phase);
propane in the polymerization system = propane in the gas phase +.1000+ propane in the liquid phase;
Total monomer inventory of polymerization system = inventory of ethylene in polymerization system + inventory of propylene in polymerization system + inventory of propane in polymerization system.
According to a specific embodiment of the present invention, preferably, the vapor-liquid equilibrium coefficients of ethylene, propylene, propane are obtained according to the following formula:
K ethylene =xc2 × (1/A) × exp(yc2/B)+0.5；
K Propylene = xc3 × (1/A+0.1) × exp(yc3/B)；
K Propane = xc30 × (1/A+0.0125) × exp(yc30/B)；
Wherein:
k is a gas-liquid equilibrium coefficient related to the solubility of the monomer in the solvent as a function of temperature and pressure;
xc2, yc2, xc3, yc3, xc30, yc30 are coefficients of ethylene, propylene, and propane, and the value ranges are respectively: xc2=1800 to 2800; yc2= -690 to-1450; xc3=1000 to 2000; yc3= -1000 to-1960; xc30=1700 to 2700; yc30= -1000 to-2100;
a=polymerization pressure value/98.0665+1.033, wherein the polymerization pressure value is in units of kPa; b is a polymerization temperature value of +230, and the unit of the polymerization temperature value is ℃.
According to a specific embodiment of the present invention, preferably, when the gas phase contains hydrogen and nitrogen, the amount of hydrogen and nitrogen present is calculated according to the following formula:
hydrogen in gas phase at put = V Air flow ×AT H 2 ÷100×PT
Nitrogen in gas phase at set quantity = V Air flow ×AT N 2 ÷100×PT
Wherein:
the unit of the hydrogen in the gas phase and the nitrogen in the gas phase is Nm 3 ；
AT H 2 Is the mole percent of hydrogen in the gas phase;
AT N 2 is the mole percent of nitrogen in the gas phase.
According to a specific embodiment of the present invention, preferably, the mole fraction weighted molecular weight of the total components (i.e., ethylene, propylene, propane, and hexane as solvent) in the liquid phase is calculated according to the following formula:
W=28 × X ethylene +42× X Propylene +44 × X Propane +86 ×(100-X Ethylene -X Propylene -X Propane )。
According to a specific embodiment of the present invention, preferably, the process system employed for the reaction in the solution process olefin polymerization reaction system comprises:
a monomer input device, a catalyst input device, a solvent input device, a reactor and a monomer separation tower;
a first mixer, a second mixer, a third mixer;
a first gas-liquid separation tank and a second gas-liquid separation tank;
a first cooler and a second cooler;
the first condenser, the second condenser and the third condenser;
a first condensate receiving tank and a second condensate receiving tank;
a first heater and a second heater;
a first compressor and a second compressor;
a condensate pump, a gel filter, a tower bottom pump and a reflux pump;
Wherein,,
the monomer input device is connected with the inlet of the first mixer, the catalyst input device is connected with the inlet of the third mixer, and the solvent input device is respectively connected with the inlet of the first mixer, the inlet of the second mixer and the inlet of the third mixer;
the outlet of the first mixer is connected with the inlet of the first cooler, and the outlet of the first cooler is connected with the inlet of the reactor; the outlet of the second mixer and the outlet of the third mixer are respectively connected with the inlet of the reactor;
the top outlet of the reactor is connected with the inlet of the first condenser (for discharging monomer gas which does not participate in the reaction and a small amount of vaporized solvent), the outlet of the first condenser is connected with the inlet of the first gas-liquid separation tank, the liquid outlet of the first gas-liquid separation tank is connected with the inlet of the condensate pump, the outlet of the condensate pump is connected with the inlet of the first mixer, the gas outlet of the first gas-liquid separation tank is connected with the inlet of the first compressor, the outlet of the first compressor is connected with the inlet of the second condenser, the outlet of the second condenser is connected with the inlet of the first condensate receiving tank, the gas outlet of the first condensate receiving tank is connected to a pipe network outside the system, and the liquid outlet of the first condensate receiving tank is connected with the inlet of the first mixer (for inputting a mixture of propylene and SOL (solvent) to the first mixer);
The bottom outlet of the reactor is connected with the inlet of the middle part of the monomer separation tower, the top outlet of the monomer separation tower is connected with the inlet of the second cooler, the outlet of the second cooler is connected with the inlet of the second gas-liquid separation tank, the liquid outlet of the second gas-liquid separation tank is connected with the inlet of the reflux pump, the outlet of the reflux pump is connected with the inlet of the first mixer, the gas outlet of the second gas-liquid separation tank is connected to a pipe network outside the system and/or is connected with the inlet of the second compressor, the outlet of the second compressor is connected with the inlet of the third condenser, the outlet of the third condenser is connected with the inlet of the second condensate receiving tank, the liquid outlet of the second condensate receiving tank is connected with the inlet of the first mixer, and the gas outlet of the second condensate receiving tank is respectively connected with the pipe network outside the system and the inlet of the first mixer;
the bottom outlet of the monomer separation tower is connected with the inlet of the gel filter, the outlet of the gel filter is connected with the inlet of the tower bottom pump (preferably, the top of the filter is the same as the bottom elevation of the monomer separation tower, and the bottom of the filter is higher than the inlet of the tower bottom pump), the outlet of the tower bottom pump is connected with the inlet of the second heater, and the outlet of the second heater is connected with the bottom inlet of the monomer separation tower;
The top outlet of the monomer separation tower is connected with the inlet of the second cooler, and the outlet of the second cooler is connected with the inlet of the second gas-liquid separation tank;
the top and the bottom of the monomer separation tower are respectively provided with a first solvent input pipeline and a second solvent input pipeline, wherein the second solvent input pipeline is provided with a first heater; the solvent inlet of the first heater is connected with the solvent input device.
According to a specific embodiment of the invention, preferably, in the above-mentioned process system, each line may be provided with means of valves, flow meters, level meters, thermometers, pressure gauges, etc. And the valves on the partial flowmeter, the liquid level meter and the corresponding pipelines can be connected, and the flowmeter and the liquid level meter are used for controlling the opening and closing of the valves so as to control the flow and the liquid level.
According to a specific embodiment of the present invention, preferably, in the above-mentioned process system, the reactor is used for carrying out the polymerization reaction, which is provided with a corresponding flow meter. The reactor may be provided with a stirrer, in particular with reference to the known manner.
According to a specific embodiment of the present invention, preferably, in the above-mentioned process system, the first gas-liquid separation tank is used for effecting gas-liquid separation of condensed products of gas from the top of the reactor (condensed by the first condenser), wherein the gas exits from the top outlet, returns to the reactor after compression and condensation, and the liquid exits from the bottom and returns to the reactor.
According to a specific embodiment of the present invention, preferably, in the above-described process system, a monomer separation column is used for separation of reaction products of polymerization reaction from the reactor, wherein the monomer is separated from the top, discharged, returned to the reactor after gas-liquid separation (through a second gas-liquid separation tank), and the copolymer (i.e., the product of polymerization reaction) enters a gel filter to remove gel by filtration, and then outputted through a bottom pump. Preferably, the top of the monomer separation column is provided with a solvent inlet for injecting solvent when needed. During the polymerization reaction, gel is a major component of the by-product. Gels are a cross-linking substance that is insoluble in solvents and, if left in the copolymer, can seriously affect the quality of the copolymer. In the process system, the installation position of the gel filter is different from other processes, and gel can be thoroughly removed. The gel is a soft small particle with a specific gravity smaller than that of the solution, and is easy to float on the upper part of the filter. After the gel filter is arranged on the bottom pump, the turbulence degree of the liquid in the gel filter can be increased, soft gel particles are deformed and discharged from the outlet of the gel filter under the action of pressure difference, and the filtering effect is seriously reduced. In the process system of the invention, the gel filter is arranged before the pump (bottom pump), and polymer overflows into the gel filter, so that most gel is accumulated in the gel filter by the filtering process, and the filtering effect can be effectively improved.
According to a specific embodiment of the present invention, preferably, in the above process system, the monomer input means includes an H input line (hydrogen input line), an ETH input line (ethylene input line), a PRO input line (propylene input line), and an ENB input line (ethylidene norbornene input line), and each line may be provided with a flow meter, respectively. The process system is suitable for producing ethylene propylene rubber, ethylene propylene diene monomer and the like, wherein when more than three monomers are adopted, a third monomer, a fourth monomer and the like can enter the system through an ENB input pipeline.
According to a specific embodiment of the present invention, preferably, in the above-mentioned process system, the catalyst input device includes a CAT input line (main catalyst injection line), an ETA input line (activator input line), and a CCD input line (cocatalyst injection line, CCD means cocatalyst diluted with solvent), and each line may be provided with a flow meter, respectively.
According to a specific embodiment of the present invention, preferably, in the above-mentioned process system, the solvent input means comprises a SOL input line, which may be provided with a flow meter.
According to a specific embodiment of the present invention, preferably, in the above-described process system, a first mixer is used to achieve mixing of the monomer (H input line, ETH input line, PRO input line, ENB input line) and the solvent (SOL input line), a second mixer is used to achieve mixing of the cocatalyst and the solvent, and a third mixer is used to achieve mixing of the main catalyst and the solvent.
According to a specific embodiment of the invention, preferably, the process system further comprises a gas chromatograph connected to a connecting line between the top outlet of the reactor and the inlet of the first condenser. More preferably, the gas chromatograph is further connected to a connecting line between the flow meter on the H input line, the flow meter at the gas outlet of the first condensate receiving tank, the top outlet of the reactor and the inlet of the first condenser. The output of the gas chromatograph controls the flow of the H-input line, the flow out of the top of the reactor (the flow into the first condenser), the flow of the gas phase outlet of the first condensate receiving tank, and these three flows change the flow simultaneously according to the measurement value of the gas chromatograph. The molar content of monomer (including the main inert) in the gas phase at the top of the reactor can be obtained by chromatography.
According to a specific embodiment of the invention, the process system preferably further comprises a reactor top discharge gas phase flow meter FI connected to a flow meter on said ETH input line, a connection line between the top outlet of said reactor and the inlet of said first condenser, a flow meter on said CAT input line, a flow meter on said ETA input line. The top discharge gas phase flow meter FI of the reactor is connected with each flow regulating valve through a meter signal line, and the output signal of the top discharge gas phase flow meter FI of the reactor is sent to each flow regulating valve. The measurement of the reactor top discharge gas phase flow meter FI also has an influence on the H-input line flow, the flow out of the top of the reactor (flow into the first condenser), the flow out of the gas phase outlet of the first condensate receiving tank and other flows into the reactor. The top discharge gas flow meter FI of the reactor was not connected to the chromatograph.
According to a specific embodiment of the present invention, preferably, in the above process system, the first cooler, the second cooler, the first condenser, the second condenser, and the third condenser are respectively provided with cooling water channels, and a thermometer may be disposed on outlet pipes of the coolers and the condensers, and the thermometer is used for detecting temperature and is connected with a valve on the cooling water channels, and is used for adjusting cooling water flow according to the temperature of the process materials, so as to maintain the stability of the temperature of the process materials. For a specific arrangement, reference may be made to a conventional cooler, condenser.
According to a specific embodiment of the present invention, preferably, in the above process system, the first compressor and the second compressor are both reciprocating compressors.
According to a specific embodiment of the present invention, preferably, in the above-mentioned process system, the second condensate receiving tank is provided with a level gauge for monitoring the level of liquid in the second condensate receiving tank.
According to a specific embodiment of the invention, preferably in the above-mentioned process system, the outlet of the bottom pump is connected to equipment outside the process system for feeding the glue solution to the subsequent unit, in addition to the inlet of the second heater. When the glue solution passing through the bottom pump has higher monomer content and higher glue solution viscosity, the bottom pump is adopted to convey the glue solution to the second heater for heating, then the glue solution returns to the monomer separation tower, when the glue solution (copolymerization product) of the bottom pump meets the requirement, the glue solution can be conveyed to a subsequent unit, and the circulation of the glue solution between the second heater and the monomer separation tower and the conveying of the glue solution to the subsequent unit are simultaneously and continuously carried out.
According to a specific embodiment of the present invention, preferably, in the above process system, the top outlet of the second gas-liquid separation tank is further connected to an external flare pipe network, and a valve is provided on the connecting pipe, and is connected to a flow meter provided at the front end of the second compressor, and is controlled by the flow meter, and the flow rate of the gas discharged to the outside of the system is set according to the produced brand, production load, and variation in gas composition.
According to a specific embodiment of the invention, preferably, in the above process system, the second condensate receives the gas in a tank, one part of which is discharged into a flare network by flow control and the other part of which is returned to the reactor by pressure control. The liquid in the second condensate receiving tank is returned to the reactor under pressure via liquid level control.
According to a specific embodiment of the present invention, preferably, the process method adopted for the reaction in the solution process olefin polymerization reaction system comprises:
polymerizing ethylene, propylene, hydrogen, nitrogen, catalyst (including main catalyst, cocatalyst and activator) and solvent in a reactor;
controlling the temperature, pressure, liquid level and reactor exhaust gas flow of the reactor; evaporating a part of monomers and solvent from the reactor by utilizing the heat of polymerization reaction, and returning the condensed monomers and solvent to the reactor;
And (3) allowing the polymer obtained by the reaction to enter a monomer separation tower, evaporating unreacted monomers, and returning the evaporated monomers to the reactor to participate in the reaction.
The technological process provided by the invention can adopt a solution polymerization process, the solvent is linear alkane, the main polymerization reactant is two or three olefins, and the main equipment is a polymerization reactor with a stirrer, a monomer separation tower and two pressure reciprocating compressors. Various raw materials and catalysts are metered into a reactor, reactants, catalysts and products are dissolved in a solvent, and the products are sent to a subsequent working section after gel is separated out by a gel filter; unreacted monomers are recycled back to the reactor after being boosted by the compressor to continue to participate in the polymerization reaction; the polymerization reaction is exothermic, and the reaction heat is removed from the reactor by evaporating the monomers and solvent, condensing outside the reactor, and returning to the reactor.
According to a specific embodiment of the present invention, preferably, in the above process, the monomer comprises ethylene, propylene. The process method can also adopt a third monomer and a fourth monomer which can be ENB and dicyclopentadiene respectively.
According to a specific embodiment of the present invention, preferably, in the above process, the solvent comprises a C5-C8 linear alkane.
In the above process, the main catalyst may be formulated according to the reaction to be performed, and preferably, the catalyst is a complex formed of a titanium/vanadium-based compound (titanium or vanadium-based compound) and an alkylaluminum soluble in a hydrocarbon solvent.
According to a specific embodiment of the present invention, preferably, in the above process, the mass ratio of the titanium/vanadium compound to the aluminum alkyl is 5-15:1.
According to a specific embodiment of the present invention, preferably, in the above process, the titanium/vanadium compound comprises titanium tetrachloride and/or vanadium oxychloride.
According to a specific embodiment of the present invention, preferably, in the above process, the alkyl aluminum comprises one or a combination of two or more of triisobutyl aluminum, triethyl aluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride.
According to a specific embodiment of the present invention, preferably, in the above process, the main catalyst contains an alcohol and/or an ester; the selectivity of the catalyst can be changed by adding alcohol substances or ester substances; more preferably, the alcohol substance comprises one or more of methanol, ethanol and propanol; the esters include ethyl trichloroacetate.
According to a specific embodiment of the present invention, preferably, in the above process, the amount of the alcohol and/or ester is: the molar ratio of the alcohol substances to the titanium/vanadium compounds is 1:1; the mass ratio of the ester substance to the titanium/vanadium compound is in the range of 5-15.
According to a specific embodiment of the present invention, preferably, in the above process, the catalyst (i.e. the procatalyst) is selected from one of the following six classes:
wherein A represents titanium and vanadium;
AX represents titanium, vanadium and alcohols;
BX represents ethylaluminum dichloride;
BM represents diethylaluminum chloride;
BQ represents ethylaluminum sesquichloride;
ES stands for ester compounds.
In the reaction systems corresponding to the above six types of catalysts, the first type of the catalyst can produce compounds with higher Mooney viscosity, the second, fourth and sixth types of the catalyst can produce copolymers with narrow molecular weight distribution, and the third and fifth types of the catalyst can produce copolymers with wide molecular weight distribution. The product with wide molecular weight distribution is mainly applied to plastic modification. The product with narrow molecular weight distribution has better oil solubility and is suitable for being used as an oil product additive.
According to a specific embodiment of the present invention, preferably, in the above process, the activator (ETA) employs an ester compound, which has a main effect of increasing the activity of the main catalyst.
According to a specific embodiment of the present invention, preferably, in the above process, the cocatalyst is a metallic aluminium compound, for example an alkyl aluminium catalyst.
According to a specific embodiment of the present invention, preferably, in the above process, the main catalyst has an efficiency of 1600 to 3800 g polymer/g catalyst.
In the above process, the device is started to reach a stable operation state, preferably, the operation parameters of the key control points are as follows: the temperature in the reactor is controlled to be 30-80 ℃ (more preferably 40-60 ℃), the pressure is controlled to be 0.5-3.0MPa (preferably 0.6-1.5 MPa), and the flow rate of the solvent entering the reactor is controlled to be 30-50t/h. Wherein, the mass flow rate of each monomer component can be adjusted according to the numerical value required by the product brand formula.
In the above-mentioned process, the main factors affecting the copolymer properties are polymerization temperature, catalytic activity (i.e., catalyst efficiency), comonomer concentration ratio, concentration ratio of molecular weight regulator to comonomer, polymerization residence time, etc., which can be obtained by practical processes.
Determination of polymerization temperature:
the polymerization temperature has a large influence on the polymerization rate, the molecular weight distribution and the catalyst teaching rate, and the determination of a suitable reaction temperature has an important influence on the properties of the copolymer produced:
The catalyst activity versus temperature curve shows that the catalyst activity is inversely proportional to the polymerization temperature, and that an increase in temperature greatly reduces the solubility of the monomer in the solvent, and that the active center lifetime decreases with increasing temperature. The catalyst efficiency decreases with increasing temperature, which in turn leads to a decrease in yield, and the molecular weight of the polymer decreases with increasing temperature. According to a specific embodiment of the present invention, preferably, in the above process, the polymerization temperature is controlled to 30 to 80 ℃, more preferably 40 to 60 ℃.
Determination of comonomer ratio in polymerization System:
the ratio of the comonomers in the polymerization system directly affects the amount of each monomer incorporated into the copolymer due to the reactivity ratio difference. The individual monomer concentration variations also have a significant effect on the polymerization rate. The molar ratio of ethylene to propylene in the reactor gas phase is shown in Table 1 in relation to the ethylene content in the product.
TABLE 1
Influence of catalyst concentration:
the catalyst concentration increases, the active center increases, the polymerization reaction accelerates, but the catalyst efficiency decreases, the polymer molecular weight decreases, the mooney viscosity decreases with it, and the polymerization temperature will increase significantly due to the acceleration of the reaction rate. The mass ratio of the aluminum alkyl to the vanadium catalyst has extremely important influence on the polymerization reaction, the aluminum alkyl catalyst not only serves as a cocatalyst for alkylating metal vanadium to form an active center, but also plays a role in chain transfer and purifying trace impurities in a reaction system, when the mass ratio of the aluminum catalyst to the vanadium catalyst in the reaction system is more than 20, the polymerization reaction rate is reduced, and when the mass ratio of the aluminum catalyst to the vanadium catalyst is less than 5, a large amount of gel is generated. The single pass conversion of monomer increases with increasing catalyst concentration. In the design of the polymerization catalyst, the invention determines that the mass ratio of the aluminum catalyst to the vanadium catalyst is 7; the concentration of vanadium in the solution was 1:20 to 40 tens of thousands (weight ratio).
According to a specific embodiment of the present invention, preferably, the process further comprises the step of adding a molecular weight regulator. The molecular weight regulator is used as chain terminator in polymerization reaction to regulate molecular weight of polymer, and the molecular weight is controlled by means of the concentration ratio of molecular weight regulator to comonomer, and the different product brands correspond to different ratios, and every 0.1 change of the ratio, the Mooney viscosity of the product is changed by 3 units. More preferably, the mass ratio of the molecular weight regulator to the monomer in the reactor gas phase is 0.1 to 1.
According to a specific embodiment of the present invention, in the above-described process, the determination of the polymerization residence time is closely related to the polymerization rate and the life of the catalyst. The molecular weight reaches a relatively high value within a few minutes after the start of the reaction, after which the molecular weight of the copolymer, although increasing somewhat with increasing high molecular weight fraction, is greatly reduced in magnitude. The polymer yield increases with increasing residence time, and the molecular weight and catalyst efficiency increase slightly, but the utilization of the reactor for monomer conversion decreases. Preferably, the residence time of the polymerization reaction is from 20 minutes to 120 minutes.
According to a specific embodiment of the present invention, in the above process, the concentration of the product in the reactor liquid phase affects the yield, affects the heat transfer, mass transfer process of the polymerization reaction, affects the subsequent solvent recovery costs, affects the subsequent catalyst residue removal effect. Preferably, the concentration of the copolymer obtained in the reactor is controlled to be 5 to 18wt% during the polymerization reaction.
According to a specific embodiment of the invention, in the above process, the reactor recycle gas flow is determined according to the gas yield of the polymerization reaction and the stirring strength requirement of the reactor liquid phase. Preferably, during the polymerization reaction, the flow rate of the circulating gas in the reactor is controlled to be 1000-3000m 3 /h。
According to a specific embodiment of the present invention, preferably, in the above process, the mass specifications of the product of the polymerization reaction (i.e., copolymer) include:
the product of the polymer reaction meets the following requirements:
molecular weight distribution: mw/mn=1.2-4.8;
combining propylene mass fraction: 25-52 wt%;
mooney viscosity: ml1+4100=25-120.
In the process, various polymerization monomers, catalysts and solvents are continuously added into a reactor after being metered, the temperature, the pressure, the liquid level and the flow of discharged gas of the reactor are controlled, the polymerization reaction heat enables a part of monomers and solvents to evaporate from the reactor, and the evaporated gas is compressed and condensed and then returned to the reactor; after the polymerization reaction is completed in the reactor, the product enters a monomer separation tower, unreacted monomers are distilled out, and the distilled monomers are returned to the reactor for recycling. The method keeps the stability of working conditions and grasps the monomer placement in the polymerization reaction system in real time, and is very important for controlling the quality of products.
The method provided by the invention can accurately determine the concentration and the in-situ quantity of each monomer (including main inert substances) in the polymerization reaction system, and can accurately adjust the inlet and outlet flows of a molecular weight regulator and the like by controlling the parameters, thereby realizing automatic adjustment of the molecular weight of the product and ensuring the stability of the quality of the product.
Drawings
FIG. 1 is a schematic diagram of the structure of a process system for preparing a vinyl rubbery copolymer provided in example 1.
The main reference numerals illustrate:
a reactor 1 and a monomer separation column 2;
a first mixer 31, a second mixer 32, a third mixer 33;
a first gas-liquid separation tank 41 and a second gas-liquid separation tank 42;
a first cooler 51, a second cooler 52;
a first condenser 61, a second condenser 62, a third condenser 63;
a first condensate receiving tank 71, a second condensate receiving tank 72;
a first heater 81 and a second heater 82;
a first compressor 91 and a second compressor 92;
a condensate pump 10, a gel filter 11, a bottom pump 12, and a reflux pump 13;
a liquid level meter LC, a pressure meter PC, a flow meter FC, a thermometer TC and a reactor top discharge gas phase flow meter FI.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
This example provides a specific procedure for the preparation of a vinyl rubbery copolymer using a process system having the structure shown in FIG. 1. The process system comprises:
monomer input device: the system comprises an H input pipeline, an ETH input pipeline, a PRO input pipeline and an ENB input pipeline, wherein each pipeline is provided with a flowmeter FC;
catalyst input device: the system comprises a CAT input pipeline, an ETA input pipeline and a CCD input pipeline, wherein each pipeline is provided with a flowmeter FC;
solvent input device: comprises an SOL input pipeline, wherein the pipeline is provided with a flowmeter FC;
reactor 1: corresponding liquid level meter LC and pressure meter PC are arranged, and a stirrer is arranged;
monomer separation tower 2: a liquid level meter LC is arranged;
gas chromatograph: a connecting line connected between the top outlet of the reactor 1 and the inlet of the first condenser 61, and also with a flow meter FC on the H input line, a flow meter FC at the gas outlet of the first condensate receiving tank 71;
reactor top discharge gas flow meter FI: is connected with a flowmeter FC on an ETH input pipeline, a flowmeter FC on a PRO input pipeline, a flowmeter FC on an ENB input pipeline, a connecting pipeline between the top outlet of the reactor 1 and the inlet of the first condenser 61, a flowmeter FC on a CAT input pipeline, a flowmeter FC on an ETA input pipeline, a flowmeter FC on a CCD input pipeline and a flowmeter FC on a SOL input pipeline;
A first mixer 31, a second mixer 32, a third mixer 33;
a first gas-liquid separation tank 41, a second gas-liquid separation tank 42: respectively provided with a liquid level meter LC;
the first cooler 51 and the second cooler 52: a cooling water channel is respectively arranged, and a thermometer TC is arranged on an outlet pipeline of the first cooler 51, is used for detecting temperature and is connected with a valve on the cooling water channel so as to control the flow of cooling water;
a first condensate receiving tank 71, a second condensate receiving tank 72: the two are respectively provided with a liquid level meter LC;
a first heater 81 and a second heater 82;
the first compressor 91 and the second compressor 92: are all reciprocating compressors;
a condensate pump 10, a gel filter 11, a bottom pump 12, and a reflux pump 13;
wherein,,
the monomer input device is connected with the inlet of the first mixer 31, the catalyst input device is connected with the inlet of the third mixer 33, and the solvent input device is respectively connected with the inlet of the first mixer 31, the inlet of the second mixer 32 and the inlet of the third mixer 33;
The outlet of the first mixer 31 is connected to the inlet of the first cooler 51, and the outlet of the first cooler 51 is connected to the inlet of the reactor 1; the outlet of the second mixer 32 and the outlet of the third mixer 33 are connected with the inlet of the reactor 1, and the two are combined into one pipeline and then connected with the inlet of the reactor 1;
the top outlet of the reactor 1 is connected with the inlet of the first condenser 61, the outlet of the first condenser 61 is connected with the inlet of the first gas-liquid separation tank 41, the liquid outlet of the first gas-liquid separation tank 41 is connected with the inlet of the condensate pump 10 (a valve is arranged on the connecting pipe and is connected with the liquid level meter LC of the first gas-liquid separation tank 41 to realize the liquid level control in the first gas-liquid separation tank), the outlet of the condensate pump 10 is connected with the inlet of the first mixer 31, the gas outlet of the first gas-liquid separation tank 41 is connected with the inlet of the first compressor 91 (a valve is arranged on the connecting pipe and is controlled by the pressure meter PC of the reactor 1), the outlet of the first compressor 91 is connected with the inlet of the second condenser 62, the outlet of the second condenser 62 is connected with the inlet of the first condensate receiving tank 71, the gas outlet of the first condensate receiving tank 71 is respectively connected to the pipe network outside the system and the inlet of the first mixer 31, and the liquid outlet of the first condensate receiving tank 71 is connected with the inlet of the first mixer 31 (a valve is arranged on the connecting pipe and is controlled by the liquid level meter LC of the first condensate receiving tank 71);
The bottom outlet of the reactor 1 is connected with the inlet of the middle part of the monomer separation tower 2, the top outlet of the monomer separation tower 2 is connected with the inlet of the second cooler 52, the outlet of the second cooler 52 is connected with the inlet of the second gas-liquid separation tank 42, the liquid outlet of the second gas-liquid separation tank 42 is connected with the inlet of the reflux pump 13 (a valve is arranged on a connecting pipe of the two, the valve is controlled by a liquid level meter LC of the second gas-liquid separation tank 42), the outlet of the reflux pump 13 is connected with the inlet of the first mixer 31, the gas outlet of the second gas-liquid separation tank 42 is connected with a pipe network outside the system and/or is connected with the inlet of the second compressor 92 (a valve is arranged on a connecting pipe of the top outlet of the second gas-liquid separation tank 42 and an external pipe network, the valve is connected with a pressure gauge PC arranged at the front end of the second compressor 92 and controlled by the pressure gauge PC, the outlet of the second compressor 92 is connected with the inlet of the third condenser 63, the outlet of the third condenser 63 is connected with the inlet of the second condensate receiving tank 72, the liquid outlet of the second condensate receiving tank 72 is connected with the inlet of the first mixer 31 (the valve is arranged on the connecting pipeline of the two, and is controlled by a liquid level meter LC of the second condensate receiving tank 72), and the gas outlet of the second condensate receiving tank 72 is respectively connected with a flare pipe network outside the system and the inlet of the first mixer 31;
The bottom outlet of the monomer separation tower 2 is connected with the inlet of a gel filter 11, the outlet of the gel filter 11 is connected with the inlet of a tower bottom pump 12, the outlet of the tower bottom pump 12 is connected with the inlet of a second heater 82 and is also connected with equipment outside the process system (a valve is arranged on a connecting pipeline of the two, and is controlled by a liquid level meter of the monomer separation tower 2 to control the glue solution to be delivered to the equipment outside the system), and the outlet of the second heater 82 is connected with the bottom inlet of the monomer separation tower 2; the top outlet of the monomer separation tower 2 is connected with the inlet of a second cooler 52, and the outlet of the second cooler 52 is connected with the inlet of a second gas-liquid separation tank 42;
the top and the bottom of the monomer separation tower 2 are respectively provided with a first solvent input pipeline and a second solvent input pipeline, wherein the first solvent input pipeline is provided with a flowmeter FC, and the second solvent input pipeline is provided with a first heater 81; the solvent inlet of the first heater 81 is connected with the SOL input pipeline, and a flowmeter is arranged on the connecting pipeline of the solvent inlet and the SOL input pipeline;
the first heater 81 and the second heater 82 are provided with steam input pipelines in half for providing heat; wherein, a valve is arranged on the steam input pipeline of the first heater 81 and controlled by a thermometer TC at the outlet of the first heater 81, and a valve is arranged on the steam input pipeline of the second heater 82 and controlled by a thermometer TC at the outlet of the second heater 82;
The pipeline connected with the flare network outside the system is communicated with the pipeline entering the bottom of the reactor 1.
Example 2
This example provides a process for determining parameters in a process for preparing a vinyl rubbery copolymer using the system of example 1, comprising the steps of:
feeding a 01 st material flow formed by mixing comonomer, catalyst, solvent and the like into a reactor 1 for reaction;
the monomer gas which is discharged from the top outlet of the reactor 1 and does not participate in the reaction and a small amount of vaporized solvent sequentially enter a first condenser 61 and a first gas-liquid separation tank 41 for gas-liquid separation;
the gas separated by the first gas-liquid separation tank 41 is pressurized by the first compressor 91 to form a 04 th material flow, enters the second condenser 62, then enters the first condensate receiving tank 71, the liquid in the first condensate receiving tank 71 is used as a 06 th material flow to be converged into a 011 th material flow, and the gas in the first condensate receiving tank 71 is used as a 05 th material flow to be fed into an external flare pipe network;
the liquid separated by the first gas-liquid separation tank 41 is mixed with the 06 th material flow from the first condensate receiving tank 71, the material flow from the reflux pump 13 and the material flow from the second condensate receiving tank 72 through the condensate pump 10 to form 011 th material flow; the 011 stream and the additional solvent are mixed in a first mixer 31 to form a 02 stream which enters a reactor 1 to participate in the reaction;
The 03 th material flow discharged from the bottom outlet of the reactor 1 enters the monomer separation tower 2 for separating unreacted monomers, each heater at the bottom of the tower is used for heating a medium entering the bottom of the tower, the tower bottom pump 12 has two functions, namely, the glue solution is sent to a subsequent working section, and the glue solution with higher viscosity is forced to circulate after passing through the heater and then enters the monomer separation tower 2. The glue solution is conveyed to a second heater 82 by adopting a bottom pump 12 for heating, then returned to the monomer separation tower 2, and can be taken as a 08-th material flow to be sent to a subsequent unit when the glue solution (copolymerization product) of the bottom pump 12 meets the requirement; the circulation of the glue solution in the glue solution passing through the bottom pump 12 between the second heater 82 and the monomer separation tower 2 is continuously performed simultaneously with the conveyance of the backward unit;
the gas 07 flow at the top of the monomer separation tower 2 enters the second cooler 52 for cooling, then enters the second gas-liquid separation tank 42 for separation, the liquid part obtained by the second gas-liquid separation tank 42 is converged into the 011 flow through the reflux pump 13, the gas product obtained by the second gas-liquid separation tank 42 enters the second compressor 92 for pressurization to form the 09 flow, then enters the second condensate receiving tank 72 after being condensed by the second condenser 62, and the gas product obtained by the separation of the second gas-liquid separation tank 42 can also directly enter the second condensate receiving tank 72.
The gas in the second condensate receiving tank 72 is discharged into a flare pipe network through the 010 th material flow by one part through flow control, and the other part is returned to the reactor 1 through pressure control; the liquid in the second condensate receiving tank 72 is level controlled and returned under pressure to reactor 1 via stream 011. Specific process stream data are shown in table 2:
table 2 process stream data for example 2
Note that: comonomer 1 is ethylene; comonomer 2 is propylene; comonomer 3 is ENB; comonomer 4 is dicyclopentadiene.
The specification ranges of the products of the polymerization reaction are as follows:
molecular weight distribution: mw/mn=1.5-4;
combining propylene mass fraction: 28-45wt%;
mooney viscosity: ml1+4100=30-125.
Example 3
The present example provides a method for real-time confirmation of mole percentages and in-situ quantities of various monomers in gas and liquid phases in a solution-process olefin polymerization reaction system, which is an olefin polymerization system using ethylene and propylene as raw materials and using a carbon 6 linear olefin as a solvent, wherein the determination process of relevant data of the real-time confirmation method comprises (relevant data are shown in table 3):
(1) Obtaining a mole percentage ATc of ethylene in the gas phase, a mole percentage ATc of propylene in the gas phase, and a mole percentage ATc of propane in the gas phase;
(2) Obtaining the mole percent of ethylene, propylene, propane in the liquid phase according to the mole percent of ethylene, propylene, propane (inert substance) in the gas phase, wherein:
X ethylene =ATc2÷K Ethylene ；
X Propylene =ATc3÷K Propylene ；
X Propane = ATc30÷K Propane ；
Wherein X is Ethylene 、X Propylene 、X Propane Represents the mole percent of ethylene, propylene and propane in the liquid phase, and the unit is mol%;
K ethylene （Kc2）、K Propylene （Kc3）、K Propane (Kc 30) represents vapor-liquid equilibrium coefficients of ethylene, propylene and propane, respectively, and is obtained by the following formulas:
K ethylene =xc2 × (1/A) × exp(yc2/B)+0.5；
K Propylene = xc3 × (1/A+0.1) × exp(yc3/B)；
K Propane = xc30 × (1/A+0.0125) × exp(yc30/B)；
Wherein:
xc2, yc2, xc3, yc3, xc30, yc30 are coefficients of ethylene, propylene, and propane, and the value ranges are respectively: xc2=1800 to 2800; yc2= -690 to-1450; xc3=1000 to 2000; yc3= -1000 to-1960; xc30=1700 to 2700; yc30= -1000 to-2100;
a=polymerization pressure value/98.0665+1.033, wherein the polymerization pressure value is in units of kPa; b is a polymerization temperature value of +230, and the unit of the polymerization temperature value is DEG C;
(3) Obtaining the in-situ amount of ethylene, propylene and propane in the gas phase according to the mole percent of the ethylene, propylene and propane in the gas phase, wherein:
ethylene in the gas phase in the amount of C2 (G) =v Air flow ×ATc2÷100×PT×28÷22.4；
Propylene in gas phase in the amount of C3 (G) =v Air flow ×ATc3÷100×PT×42÷22.4；
The amount of propane in the gas phase C30 (G) =v Air flow ×ATc3÷100×PT×44÷22.4；
Hydrogen in gas phase in quantity H 2 (G)= V Air flow ×AT H 2 ÷100×PT；
Nitrogen in gas phase in quantity N 2 (G)= V Air flow ×AT N 2 ÷100×PT；
Wherein:
the unit of the amount of ethylene, propylene and propane in the gas phase is kg;
V air flow Representing the volume of the gas phase in the reactor, in particular 24.8m 3 ；
PT is a temperature-pressure compensation coefficient, pt= (a×273)/(1.033× (b+273));
the unit of the hydrogen in the gas phase and the nitrogen in the gas phase is Nm 3 ；
AT H 2 Is the mole percent of hydrogen in the gas phase;
AT N 2 is the mole percent of nitrogen in the gas phase;
(4) Obtaining the in-situ amount of ethylene, propylene and propane in the liquid phase according to the mole percent of the ethylene, propylene and propane in the liquid phase, wherein:
ethylene in liquid phase in amount C2 (L) =v Liquid and its preparation method ×ρ Liquid and its preparation method ×28×W；
Propylene in liquid phase in amount C3 (L) =v Liquid and its preparation method ×ρ Liquid and its preparation method ×42×W；
The amount of propane in the liquid phase C30 (L) =v Liquid and its preparation method ×ρ Liquid and its preparation method ×44×W；
Wherein:
the unit of the amount of ethylene, propylene and propane in the liquid phase is ton;
V liquid and its preparation method For the working volume of the liquid phase in the reactor, in particular 37.2m 3 ；
ρ Liquid and its preparation method Is of liquid phase density, in particular 06 tons/m 3 ；
W=28 × X Ethylene +42× X Propylene +44 × X Propane +86 ×(100-X Ethylene -X Propylene -X Propane )；
(5) Obtaining the in-situ amount of ethylene, propylene and propane in the polymerization reaction system and the total monomer in the polymerization reaction system according to the in-situ amount of ethylene, propylene and propane in the gas phase and the in-situ amount of ethylene, propylene and propane in the liquid phase, wherein:
Ethylene in the polymerization system = ethylene in the gas phase +.1000+ ethylene in the liquid phase;
propylene in the polymerization system = propylene in the gas phase/(1000 + propylene in the liquid phase);
propane in the polymerization system = propane in the gas phase +.1000+ propane in the liquid phase;
total monomer inventory of polymerization system = inventory of ethylene in polymerization system + inventory of propylene in polymerization system + inventory of propane in polymerization system.
TABLE 3 Table 3
In the actual reaction process, the gas chromatograph can obtain the mole percentages of the monomer, inert substances and solvents in the gas phase at any time, then the mole percentages and the in-situ quantities of the monomer, the inert substances in the gas phase and the liquid phase can be determined in real time by the method, and the quantities of the monomer, the molecular weight regulator and the like entering the reactor can be controlled in real time according to the results, so that the control of the polymerization degree is realized, the polymerization reaction can be stably carried out, and the stability of the product quality is ensured.
Claims (15)
1. A method for real-time confirmation of mole percentages and in-situ quantities of various monomers in gas and liquid phases in a solution-process olefin polymerization reaction system comprises the following steps:
(1) Obtaining the mole percent of each monomer in the gas phase;
(2) Obtaining mole percentages of the various monomers in the liquid phase from mole percentages of the various monomers in the gas phase, wherein mole percentages of the monomers in the liquid phase = mole percentages of the monomers in the gas phase ≡vapor-liquid equilibrium coefficient of the monomers;
(3) Obtaining the placed amount of each monomer in the gas phase according to the mole percent of each monomer in the gas phase, wherein the placed amount of each monomer in the gas phase = the gas phase volume of the reactor x the mole percent of each monomer in the gas phase x the temperature pressure compensation coefficient x the mole mass of the corresponding monomer ≡22.4;
(4) Obtaining the in-place amount of each monomer in the liquid phase according to the mole percent of each monomer in the liquid phase, wherein the in-place amount of each monomer in the liquid phase = the liquid phase working volume of the reactor x the liquid phase density x the mole mass of each monomer x the mole percent of each monomer in the liquid phase ≡total component mole fraction weighted molecular weight in the liquid phase;
(5) Obtaining the in-situ quantity of each monomer in the polymerization reaction system and the total monomer in the polymerization reaction system according to the in-situ quantity of each monomer in the gas phase and the in-situ quantity of each monomer in the liquid phase;
The process system adopted in the reaction in the solution method olefin polymerization reaction system comprises the following steps:
a monomer input device, a catalyst input device, a solvent input device, a reactor (1) and a monomer separation tower (2);
a first mixer (31), a second mixer (32), a third mixer (33);
a first gas-liquid separation tank (41) and a second gas-liquid separation tank (42);
a first cooler (51) and a second cooler (52);
a first condenser (61), a second condenser (62), and a third condenser (63);
a first condensate receiving tank (71), a second condensate receiving tank (72);
a first heater (81) and a second heater (82);
a first compressor (91) and a second compressor (92);
a condensate pump (10), a gel filter (11), a tower bottom pump (12) and a reflux pump (13);
wherein,,
the monomer input device is connected with the inlet of the first mixer (31), the catalyst input device is connected with the inlet of the third mixer (33), and the solvent input device is respectively connected with the inlet of the first mixer (31), the inlet of the second mixer (32) and the inlet of the third mixer (33);
The outlet of the first mixer (31) is connected with the inlet of the first cooler (51), and the outlet of the first cooler (51) is connected with the inlet of the reactor (1); the outlet of the second mixer (32) and the outlet of the third mixer (33) are respectively connected with the inlet of the reactor (1);
the top outlet of the reactor (1) is connected with the inlet of the first condenser (61), the outlet of the first condenser (61) is connected with the inlet of the first condensate receiving tank (71), the liquid outlet of the first condensate receiving tank (71) is connected with the inlet of the condensate pump (10), the outlet of the condensate pump (10) is connected with the inlet of the first mixer (31), the gas outlet of the first condensate receiving tank (41) is connected with the inlet of the first compressor (91), the outlet of the first compressor (91) is connected with the inlet of the second condenser (62), the outlet of the second condenser (62) is connected with the inlet of the first condensate receiving tank (71), the gas outlet of the first condensate receiving tank (71) is connected to a pipe network outside the system, and the liquid outlet of the first condensate receiving tank (71) is connected with the inlet of the first mixer (31);
The bottom outlet of the reactor (1) is connected with the inlet of the middle part of the monomer separation tower (2), the top outlet of the monomer separation tower (2) is connected with the inlet of the second cooler (52), the outlet of the second cooler (52) is connected with the inlet of the second condensate receiving tank (72), the liquid outlet of the second condensate receiving tank (72) is connected with the inlet of the reflux pump (13), the outlet of the reflux pump (13) is connected with the inlet of the first mixer (31), the gas outlet of the second condensate receiving tank (42) is connected to a pipe network outside the system and/or is connected with the inlet of the second compressor (92), the outlet of the second compressor (92) is connected with the inlet of the third condenser (63), the outlet of the third condenser (63) is connected with the inlet of the second condensate receiving tank (72), the liquid outlet of the second condensate receiving tank (72) is connected with the inlet of the first mixer (31), and the condensate outlet of the second compressor (92) is connected with the inlet of the first mixer (31), respectively;
the bottom outlet of the monomer separation tower (2) is connected with the inlet of the gel filter (11), the outlet of the gel filter (11) is connected with the inlet of the tower bottom pump (12), the outlet of the tower bottom pump (12) is connected with the inlet of the second heater (82), and the outlet of the second heater (82) is connected with the bottom inlet of the monomer separation tower (2);
The top and the bottom of the monomer separation tower (2) are respectively provided with a first solvent input pipeline and a second solvent input pipeline, wherein the second solvent input pipeline is provided with a first heater (81); the solvent inlet of the first heater (81) is connected to the solvent input device.
2. The real-time confirmation method according to claim 1, wherein in step (1), the mole percentage of the monomer in the gas phase is obtained by gas chromatography.
3. The real-time validation method according to claim 1, wherein in step (3), the temperature-pressure compensation coefficient is obtained by the following formula:
temperature-pressure compensation coefficient= (a×273)/(1.033× (polymerization temperature value +273));
wherein a = polymerization pressure value/98.0665+1.033, wherein the polymerization pressure value is in kPa; the polymerization temperature values are in units of ℃.
4. The real-time validation method of claim 1, wherein in step (4), the total component mole fraction weighted molecular weight in the liquid phase is the sum of the product of the molar mass of each component and the mole percent of each component, the components including monomers, inerts, and solvents.
5. The real-time confirmation method according to claim 1, wherein in the step (5), the amount of each monomer present in the polymerization reaction system is obtained by the following formula:
The amount of each monomer in the polymerization reaction system = the amount of the monomer in the gas phase + the amount of the monomer in the liquid phase;
the total monomer placement amount of the polymerization reaction system is the sum of the placement amounts of the monomers in the polymerization reaction system.
6. The method according to claim 1, wherein the solution-process olefin polymerization reaction system is an olefin polymerization system using ethylene and propylene as raw materials and hexane as a solvent, and the method comprises:
(1) Obtaining a mole percentage ATc of ethylene in the gas phase, a mole percentage ATc of propylene in the gas phase, and a mole percentage ATc of propane in the gas phase;
(2) Obtaining the mole percent of ethylene, propylene and propane in the liquid phase according to the mole percent of ethylene, propylene and propane in the gas phase, wherein:
X ethylene =ATc2÷K Ethylene ；
X Propylene =ATc3÷K Propylene ；
X Propane = ATc30÷K Propane ；
Wherein X is Ethylene 、X Propylene 、X Propane Respectively represent ethylene, propylene and propyleneThe mole percent of alkane in the liquid phase, in mol%;
K ethylene 、K Propylene 、K Propane Respectively representing the vapor-liquid equilibrium coefficients of ethylene, propylene and propane;
(3) Obtaining the in-situ amount of ethylene, propylene and propane in the gas phase according to the mole percent of the ethylene, propylene and propane in the gas phase, wherein:
Ethylene in the gas phase in the quantity=v Air flow ×ATc2÷100×PT×28÷22.4；
Propylene in gas phase in quantity=v Air flow ×ATc3÷100×PT×42÷22.4；
Propane in gas phase in quantity=v Air flow ×ATc3÷100×PT×44÷22.4；
Wherein:
the unit of the amount of ethylene, propylene and propane in the gas phase is kg;
V air flow Representing the volume of the gas phase in the reactor, in m 3 ；
PT is a temperature-pressure compensation coefficient, pt= (a×273)/(1.033× (b+273));
a=polymerization pressure value/98.0665+1.033, wherein the polymerization pressure value is in units of kPa; b is a polymerization temperature value, and the unit is DEG C;
(4) Obtaining the in-situ amount of ethylene, propylene and propane in the liquid phase according to the mole percent of the ethylene, propylene and propane in the liquid phase, wherein:
ethylene in liquid phase in quantity = V Liquid and its preparation method ×ρ Liquid and its preparation method ×28×W；
Propylene in liquid phase in quantity=v Liquid and its preparation method ×ρ Liquid and its preparation method ×42×W；
Propane in liquid phase in quantity = V Liquid and its preparation method ×ρ Liquid and its preparation method ×44×W；
Wherein:
the unit of the amount of ethylene, propylene and propane in the liquid phase is ton;
V liquid and its preparation method Is the working volume of the liquid phase in the reactor, the unit is m 3 ；
ρ Liquid and its preparation method Is the density of liquid phase, and the unit is ton/m 3 ；
W is the molar fraction weighted molecular weight of the total components in the liquid phase;
(5) Obtaining the in-situ amount of ethylene, propylene and propane in the polymerization reaction system and the total monomer in the polymerization reaction system according to the in-situ amount of ethylene, propylene and propane in the gas phase and the in-situ amount of ethylene, propylene and propane in the liquid phase, wherein:
Ethylene in the polymerization system = ethylene in the gas phase +.1000+ ethylene in the liquid phase;
propylene in the polymerization system = propylene in the gas phase/(1000 + propylene in the liquid phase);
propane in the polymerization system = propane in the gas phase +.1000+ propane in the liquid phase;
total monomer inventory of polymerization system = inventory of ethylene in polymerization system + inventory of propylene in polymerization system + inventory of propane in polymerization system.
7. The real-time validation method of claim 6, wherein the vapor-liquid equilibrium coefficients of ethylene, propylene, propane are obtained according to the following formula:
K ethylene =xc2 × (1/A) × exp(yc2/B)+0.5；
K Propylene = xc3 × (1/A+0.1) × exp(yc3/B)；
K Propane = xc30 × (1/A+0.0125) × exp(yc30/B)；
Wherein,,
xc2, yc2, xc3, yc3, xc30, yc30 are coefficients of ethylene, propylene, and propane, and the value ranges are respectively: xc2=1800 to 2800; yc2= -690 to-1450; xc3=1000 to 2000; yc3= -1000 to-1960; xc30=1700 to 2700; yc30= -1000 to-2100;
a=polymerization pressure value/98.0665+1.033, wherein the polymerization pressure value is in units of kPa; b is a polymerization temperature value of +230, and the unit of the polymerization temperature value is ℃.
8. The real-time confirmation method according to claim 6, wherein the amounts of hydrogen and nitrogen contained in the gas phase are calculated according to the following formula:
hydrogen in gas phase at put = V Air flow ×AT H 2 ÷100×PT
Nitrogen in gas phase at set quantity = V Air flow ×AT N 2 ÷100×PT
Wherein:
the unit of the hydrogen in the gas phase and the nitrogen in the gas phase is Nm 3 ；
AT H 2 Is the mole percent of hydrogen in the gas phase;
AT N 2 is the mole percent of nitrogen in the gas phase.
9. The real-time validation method of claim 6, wherein the total component mole fraction weighted molecular weight in the liquid phase is calculated according to the following formula:
W=28 × X ethylene +42× X Propylene +44 × X Propane +86 ×(100-X Ethylene -X Propylene -X Propane )。
10. The real-time validation method of claim 1, wherein the monomer input means comprises an H input line, an ETH input line, a PRO input line, an ENB input line, a hydrogen input line, an ethylene input line, a propylene input line, an ethylidene norbornene input line, respectively;
the catalyst input device comprises a CAT input pipeline and an ETA input pipeline, which are respectively a main catalyst injection pipeline and an activator input pipeline.
11. The real-time validation method according to claim 10, wherein the process system further comprises a gas chromatograph connected to a connection line between a top outlet of the reactor (1) and an inlet of the first condenser (61);
The gas chromatograph is also connected with a flowmeter on the H input pipeline, a flowmeter at the gas outlet of the first condensate receiving tank (71), and a connecting pipeline between the top outlet of the reactor (1) and the inlet of the first condenser (61).
12. The real-time confirmation method according to claim 9, wherein the process method adopted for the reaction in the solution-process olefin polymerization reaction system comprises:
polymerizing ethylene, propylene, hydrogen, catalyst and solvent in a reactor;
controlling the temperature, pressure, liquid level and reactor exhaust gas flow of the reactor; evaporating a part of monomers and solvent from the reactor by utilizing the heat of polymerization reaction, and returning the condensed monomers and solvent to the reactor;
and (3) allowing the polymer obtained by the reaction to enter a monomer separation tower, evaporating unreacted monomers, and returning the evaporated monomers to the reactor to participate in the reaction.
13. The real-time confirmation method according to claim 12, wherein the temperature in the reactor is controlled to be 30-80 ℃, the pressure is controlled to be 0.5-3.0MPa, and the flow rate of the solvent into the reactor is controlled to be 30-50t/h.
14. The real-time validation method of claim 12, wherein the residence time of the polymerization reaction is 20 minutes to 120 minutes.
15. The real-time confirming method according to claim 12, wherein the concentration of the resulting copolymer in the reactor is controlled to be 5 to 18wt% during the polymerization reaction.
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