CN107963999B - Method for controlling addition amount of VPO catalyst auxiliary agent water in MAH preparation process - Google Patents
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Abstract
The invention relates to a method for controlling the adding amount of VPO catalyst auxiliary agent water in an MAH preparation process, which is characterized by comprising the following steps: an atmospheric hygrothermograph and a calculation module are connected to a water control valve connected with a shell-and-tube fixed bed reactor for preparing MAH, the atmospheric hygrothermograph is used for measuring the environmental temperature T and the relative humidity RH, the measured values are input into the calculation module, and the addition amount of the auxiliary agent water is accurately controlled by formula calculation. The invention realizes the accurate control of the water amount of the catalyst bed layer addition agent, so that the humidity of the butane mixed gas entering the reactor is kept at a constant value and is not influenced by the temperature and the humidity of the environment; the high selectivity and yield of the catalyst are improved, the selectivity is improved by 2.1%, the quality yield is improved by 2.4%, and the following problems are avoided: the phosphide is concentrated at the feed end of the reactor due to the low water addition amount, so that the temperature distribution of the reactor is uneven, and the by-products are increased due to the excessive water addition.
Description
Technical Field
The invention relates to the field of catalytic oxidation of hydrocarbons with more than 4 carbon atoms, in particular to a method for accurately controlling the addition of catalyst promoter water in the process of producing maleic anhydride by using n-butane as a raw material.
Background
Maleic Anhydride (MAH) is a common basic organic chemical raw material, is the second largest anhydride raw material which is second to phthalic anhydride in the world, and downstream products of the maleic anhydride have quite wide development and application prospects. MAH is widely used in a series of important organic chemicals and fine chemicals such as synthetic resins, lubricant additives, medicines, food additives, 1, 4-butanediol, gamma-butyrolactone, tetrahydrofuran, succinic acid, fumaric acid, and the like.
The production of MAH by n-butane oxidation is carried out over a Vanadium Phosphorus Oxide (VPO) catalyst or a VPO catalyst containing a small amount of promoter, for example: contains Mo, Zn, U, W, Sn, Bi, Ti, Nb, Sb, Co, etc. The reaction is carried out on a shell-and-tube fixed bed reactor at the temperature of 400-450 ℃, the oxidation reaction is strong heat release, and the generated gas contains the product MAH and byproducts acetic acid, acrylic acid, carbon monoxide and carbon dioxide. The heat generated by the reaction is carried away by the flowing molten salt. At present, the length-diameter ratio of fixed bed reactor tubes is over 100, the cooling capacity of molten salt in the whole reactor is basically consistent, but the reaction rate changes along with the concentration of n-butane and the temperature change of a catalyst bed layer, and the reaction rate is faster and faster along with the initiation of the reaction because the temperature of n-butane mixed gas entering the bottom of the reactor is lower until the butane concentration is reduced, so that the reaction heat release is slowed down. The most violent reaction, the point with the highest heat release to make the catalyst bed temperature the highest is called the hot spot temperature, the higher the hot spot temperature is, the more by-products are generated, the higher the conversion rate is, the lower the yield is, and the selectivity is reduced. If the hot spot temperature exceeds 500 ℃ or the difference between the maximum hot spot temperature and the molten salt temperature exceeds 60 ℃, the catalyst is deactivated and the service life of the catalyst is shortened.
In order to increase the selectivity of the catalyst, decrease the activity and increase the yield, it is common in the art to add a phosphide such as trimethyl phosphate or triethyl phosphate to adjust the activity and selectivity of the catalyst. The main function of the phosphorus supplementation is to maintain the phosphorus-vanadium ratio in the VPO catalyst and to maintain the active phase (VO) for MAH formation2P2O7The proportion in the catalyst. After the addition of the phosphide, the addition of the auxiliary water is interrupted or continued, so that the added phosphide is distributed more uniformly over the catalyst bed. Zanthoff in the literature (On the active roll of water reducing partial oxidation of n-butyl to maleic anhydride over (VO)2P2O7catalysts[J]Applied Catalysts, 1998,172(1):49-58) indicate that water is present (VO)2P2O7The active phase catalyst plays an important role in the process of preparing MAH by catalyzing and oxidizing n-butane. On one hand, water can inhibit the inactive irreversible adsorption of n-butane on the VPO catalyst, and the desorption speed of reaction products is improved; on the other hand, adsorption on the water-dissociating VPO catalyst breaks the bonds V-O-V, V-O-P, or P-O-P, promoting the formation of V-OH and P-OH groups, which makes the redox reaction easier, thus making the catalyst in a highly active state when MAH is formed.
Prior patents US4701433 and US4810803 disclose introducing water and phosphide to the catalyst bed of an MAH reactor to partially deactivate the catalyst, move the hot spot downstream, deactivate the previously generated hot spot zone, and make the reactor more isothermally distributed, thereby increasing the MAH yield. The phosphorus compound comprises alkyl phosphate and alkyl phosphate, including trimethyl phosphate. The patent describes that the addition amount of phosphide is 0.005-5g/Kg per day of catalyst, the addition amount of water is 0.1-4 wt% of the mass of the mixed gas, and after trimethyl phosphate and water are added, the hot spot temperature moves downstream, thus improving the selectivity and yield of the catalyst. However, the addition of phosphide and water at any time or in any manner is not described. The patent only describes that the amount of water added is 0.1-4% of the mass of the gas mixture, and does not mention how to stabilize the humidity of the gas mixture to ensure the optimal selectivity of the catalyst.
Patent US4515899 describes a process for increasing the yield of phosphorus treated VPO catalysts by water treatment. The patent states that treatment of the catalyst with phosphide reduces activity but increases selectivity, with the loss of activity being compensated by an increase in reaction temperature. This patent found that the phosphorus compound was concentrated near the feed end of the reactor, thereby requiring a limit to the amount of phosphorus added. The phosphorus compound is redistributed more uniformly throughout the reaction zone by the addition of water after treatment with the phosphorus compound. The water addition may be a period of time after the phosphide treatment or may be immediate. The phosphide used in the method of the patent is trimethyl phosphite and trimethyl phosphate. The patent technology improves the selectivity and yield of the catalyst by adding trimethyl phosphate and then using water for treatment, but does not describe the control adding method and adding amount of water and the influence of the humidity of air on the performance of the catalyst.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a method for controlling the addition amount of auxiliary agent water of a VPO catalyst in an MAH preparation process, which can accurately control the addition amount of the auxiliary agent water, keep the humidity of butane mixed gas entering a reactor at a constant value, is not influenced by the temperature and the humidity of the environment, and improve the selectivity and the yield of the VPO catalyst.
The purpose of the invention is realized by the following technical scheme: a method for controlling the addition of VPO catalyst auxiliary agent water in the MAH preparation process is characterized in that an atmospheric hygrothermograph and a calculation control module are connected to a water control valve connected with a shell-and-tube fixed bed reactor for preparing MAH, the atmospheric hygrothermograph is used for measuring the ambient temperature T and the relative humidity RH, the measured values are input into the calculation control module, and the addition of the auxiliary agent water is accurately controlled by calculation of a formula; the calculation formula is as follows:
wherein m is3Is the amount of water replenished after removing the moisture in the air, the amount varies with the atmospheric temperature and humidity, m3Is the mass flow t/h of water added into the reactor; RH is the current atmospheric relative humidity%; c3Is the water concentration mol% of the mixed gas; t is the current atmospheric temperature; m is1Is the mass flow of air into the reactor; m is2Is the butane mass flow rate t/h; SV is the space velocity h through the reactor-1(ii) a V is the volume m of the catalyst3；M1The relative molecular weight of air is 29; m2Is a diceThe relative molecular weight of the alkane takes 58; m3The relative molecular weight of water is 18; the value range of a is 3-50, and the value range of b is 0.1-20.
Further, the atmospheric ambient temperature ranges from-50 to 50 ℃.
Further, the VPO catalyst satisfies the following formula:
(VO)2P2O7·A·B；
wherein A is VOPO4、VO(PO3)2、VO(H2PO4)、VO(HPO4)·0.5H2O、VO(HPO4)2H2O、(VO)2H4P2O9One or a combination of more of the above;
b is one or more of Fe, Co, Zr, Ni, W, Cd, Bi, Li, Hf, Mo, B, Si, U, Ba, In, Pd, Cu, Mn, Cr, Zn, Sn, Ce, Sm, Th, Nd, Y and I, II group elements In the periodic table of elements and one or more of oxides thereof.
Further, the average valence of vanadium in the VPO catalyst is between +4 and + 4.5.
Further, the additional water amount m3The molar concentration of the mixed gas is 0-5 mol%.
Furthermore, the value range of a in the formula is 3-50, and the value range of b is 0.1-20.
Still further, the number of the used temperature and humidity instruments is at least 1.
The outstanding substantive features and remarkable progress of the technical scheme of the invention are mainly reflected in that: the invention realizes the accurate control of the water amount of the catalyst bed layer addition agent added in the MAH preparation process, so that the humidity of the butane mixed gas entering the reactor is kept at a constant value and is not influenced by the temperature and the humidity of the environment; the concentration of phosphide at the feed end of the reactor caused by too low water addition is avoided, the temperature distribution of the reactor is not uniform, and the increase of byproducts caused by excessive water addition, such as maleic acid, fumaric acid, monobutyl phthalate and the like is avoided; the high selectivity and yield of the catalyst are improved, the selectivity is improved by 2.1 percent, and the mass yield is improved by 2.4 percent.
Drawings
FIG. 1 is a process flow diagram for preparing MAH using the method of the present invention; wherein the marking means: the system comprises an A-temperature and humidity instrument, a B-calculation control module, a 1-water and 2-water flow control valve, a 3-air and 4-butane gas and 5-phosphide feeder, a 6-phosphide storage tank, a 7-fixed bed reactor, an 8-phosphide atomizer and a 9-mixer.
FIG. 2 is a flow chart of a conventional process for preparing MAH; wherein the marking means: 1-water, 2-water flow control valve, 3-air, 4-butane gas, 5-phosphate feeder, 6-phosphide storage tank, 7-fixed bed reactor, 8-phosphide atomizer, 9-mixer and 10-flow controller.
Detailed Description
On one hand, water enters the bottom of the reactor in the form of steam, takes away redundant phosphide on the catalyst with the bottom firstly contacting the phosphide and redistributes the phosphide on a catalyst bed layer, and the excessive loss of activity of the catalyst due to the excessive attachment of the phosphide on the surface of the catalyst is avoided; on the other hand, inactive irreversible adsorption of n-butane on the VPO catalyst can be suppressed, increasing the desorption rate of the reaction product, thereby making the catalyst in a highly selective state when generating MAH.
In the prior art, a method for accurately controlling the water addition amount and stabilizing the humidity of mixed gas is not provided, and the problem that the selectivity of a catalyst is reduced because the humidity of butane mixed gas entering a reactor is influenced by the temperature and the humidity of the atmospheric environment in the production of MAH is solved. The invention provides a method for controlling the adding amount of VPO catalyst auxiliary agent water in an MAH preparation process, which can accurately control the adding amount of the auxiliary agent water, so that the humidity of butane mixed gas entering a reactor is kept at a constant value and is not influenced by the temperature and the humidity of the environment, and phosphide is prevented from being concentrated at the feed end of the reactor, the temperature of the reactor is uniformly distributed, a hot spot is at a reasonable position of a catalyst bed layer, and the purposes of high selectivity and high yield of a catalyst are achieved.
The humidity of the butane mixture gas entering the reactor is affected by the ambient temperature and humidity. The phosphorus is concentrated at the feed end of the reactor due to the excessively low water addition amount, and the temperature distribution of the reactor is uneven; an excess of water addition results in an increase in by-products such as maleic acid, fumaric acid, monobutyl phthalate, and the like.
Therefore, the inventor of the invention connects an atmospheric hygrothermograph and a calculation control module on a water control valve connected with a shell-and-tube fixed bed reactor for preparing MAH, the atmospheric hygrothermograph measures the environmental temperature T and the relative humidity RH, the numerical values are input into the calculation control module, and the addition amount of the auxiliary agent water is accurately controlled by formula calculation; the calculation formula is as follows:
this calculate water addition volume measures ambient temperature T, relative humidity RH through the humiture appearance, and the numerical value is carried for the computer and is calculated, then assigns water flow control valve automatically and adjusts, and water addition volume changes along with the change of environment humiture, guarantees the stability of humidity in the butane gas mixture to realize adding the accurate control of water volume and butane gas mixture humidity. The selectivity of the VPO catalyst is improved, and the yield of the MAH is improved. M in the formula3Adding catalyst water with mass flow rate t/h, RH being current atmospheric relative humidity%, C3Is the water concentration mol% of the mixed gas; t, the current atmospheric temperature and the atmospheric environment temperature change range are between-50 ℃ and 50 ℃; m is1For the mass flow of air into the reactor, m2The butane mass flow rate t/h, SV being the space velocity h through the reactor-1V is the volume m of the catalyst3，M1Is air relative molecular weight 29, M2Is a relative molecular weight of butane of 58, M3The value is 18, the value of a is in a range of 3-50, and the value of b is in a range of 0.1-20.
The foregoing process is applicable to VPO catalysts which satisfy the following formula: (VO)2P2O7·A·B；
Wherein A is VOPO4、VO(PO3)2、VO(H2PO4)、VO(HPO4)·0.5H2O、VO(HPO4)2H2O、(VO)2H4P2O9B is one or more of Fe, Co, Zr, Ni, W, Cd, Bi, Li, Hf, Mo, B, Si, U, Ba, In, Pd, Cu, Mn, Cr, Zn, Sn, Ce, Sm, Th, Nd and Y, and one or more of I, II elements In the periodic table and oxides thereof.
Preferably, the VPO catalyst has an average valence of vanadium of between +4 and + 4.5; water quantity m needs to be supplemented3The molar concentration of the mixed gas is 0-5 mol%; in the formula, the value range of a is 3-50, and the value range of b is 0.1-20; the number of the temperature and humidity instruments is at least 1.
The technical scheme of the invention is practically applied to the process flow of preparing the MAH, and as shown in figure 1, compared with the traditional MAH preparation process device, the water flow control valve 2 of the process device applying the method of the invention is sequentially connected with a calculation control module B and a temperature and humidity instrument A. The environmental temperature and the relative humidity measured by the temperature and humidity instrument A are calculated by the calculation control module B to obtain the water vapor addition m3The flow entering the reactor 7 is controlled by adjusting the steam flow control valve 2, the butane gas 4 and the phosphide 5 are mixed with the air 3, the adding point of the steam 1 is positioned in front of the mixed gas, the flow is the flow which removes the water content in the atmosphere and changes along with the change of a temperature and humidity instrument, and the stability of the humidity of the butane mixed gas is ensured.
The invention realizes the accurate control of the water amount of the catalyst bed layer addition agent, so that the humidity of the butane mixed gas entering the reactor is kept at a constant value and is not influenced by the temperature and the humidity of the environment. The concentration of phosphide at the feed end of the reactor and the uneven temperature distribution of the reactor caused by the excessively low water addition are avoided; an excess of water addition results in an increase in by-products such as maleic acid, fumaric acid, monobutyl phthalate, and the like. The high selectivity and yield of the catalysis are improved, the selectivity is improved by 2.1 percent, and the mass yield is improved by 2.4 percent.
The technical solution of the present invention is specifically described below with reference to specific examples, but this is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be considered as within the protective scope of the present invention.
Comparative example
In a 12-ten-thousand-ton/year MAH production device provided by the HUNSTMAN technology, n-butane is in a shell-and-tube type fixed bed reactor in the presence of a VPO catalyst, the height of a catalyst bed layer is 5900mm, the diameter of a catalyst tube is 25mm, the concentration of butane is 1.85 mol%, and the space velocity is 1560h-1Trimethyl phosphate (TMP) feed concentration 8ppm, reactor inlet pressure 180Kpag, water feed 800kg/h was maintained by the flow controller of FIG. 2. After the catalyst running time is from 1800 to 1848 hours, the conversion rate is increased from 83.5 percent to 83.9 percent, the selectivity is reduced from 67.9 percent to 66.9 percent, and the mass yield is from 95.8 percent to 94.9 percent; the conversion rate is 83.6 percent, the selectivity is 67.5 percent and the mass yield is 95.4 percent when the operation is carried out for 1896 hours.
Examples
In a 12-ten-thousand-ton/year MAH production device provided by the HUNSTMAN technology, n-butane is in the presence of a shell-and-tube type fixed bed reactor and a VPO catalyst, the height of a catalyst bed layer is 5900mm, the diameter of a catalyst tube is 25mm, the butane concentration is 1.85 mol%, and the space velocity is 1560h-1Trimethyl phosphate (TMP)8ppm, reactor inlet pressure 180Kpag, water was added using the process flow shown in FIG. 1, ensuring that the water concentration in the gas mixture was 2.4 mol%. The catalyst is operated for 1935 hours, the conversion rate is 83.2 percent, the mass yield is 98.2 percent, and the selectivity is 70 percent; the conversion rate is 83.2 percent, the mass yield is 98.2 percent and the selectivity is 70 percent when the operation is carried out for 1983 hours; the operation lasts for 2031 hours, the conversion rate is 83.2 percent, the mass yield is 98.2 percent, and the selectivity is 70 percent.
In summary, the temperature and humidity meter is used for measuring the ambient temperature T and the relative humidity RH, and the amount of water needed to be supplemented for maintaining a certain humidity of the mixed gas after removing the water content in the air is calculated through a formula. The method avoids the increase of by-product maleic acid in reaction products due to excessive water addition, and avoids the phenomenon that the added phosphide is unevenly distributed on the catalyst due to the excessively low water addition, so that the catalyst is seriously passivated partially and has high partial activity. The accurate control of the water addition amount is realized, and the real-time adjustment is carried out along with the change of the environmental temperature and humidity.
Claims (4)
1. A method for controlling the adding amount of VPO catalyst auxiliary agent water in the MAH preparation process is characterized by comprising the following steps: connecting an atmospheric hygrothermograph and a calculation control module on a water control valve connected with a shell-and-tube fixed bed reactor for preparing MAH, measuring the ambient temperature T and the relative humidity RH by the atmospheric hygrothermograph, inputting the measured values into the calculation control module, and accurately controlling the addition amount of the auxiliary agent water by formula calculation; the calculation formula is as follows:
wherein m is3Is the amount of water replenished after removing the moisture in the air, the amount varies with the atmospheric temperature and humidity, m3Is the mass flow t/h of water added into the reactor; RH is the current atmospheric relative humidity%; c3Is the water concentration mol% of the mixed gas; t is the current atmospheric temperature; m is1Is the mass flow of air into the reactor; m is2Is the butane mass flow rate t/h; SV is the space velocity h through the reactor-1(ii) a V is the volume m of the catalyst3；M1The relative molecular weight of air is 29; m2Is the relative molecular weight of butane, and takes 58; m3The relative molecular weight of water is 18; the value range of a is 3-50, and the value range of b is 0.1-20.
2. The method of controlling the amount of water added to a VPO catalyst promoter in the MAH production of claim 1, wherein: the atmospheric ambient temperature ranges from-50 to 50 ℃.
3. The method for controlling the amount of water added as a co-agent of VPO catalyst in the process of MAH production according to claim 1,the method is characterized in that: the additional water quantity m3The molar concentration of the mixed gas is 0-5 mol%.
4. The method of controlling the amount of water added to a VPO catalyst promoter in the MAH production of claim 1, wherein: the number of the used temperature and humidity instruments is at least 1.
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