CN113527159B - Method for utilizing refinery acid gas - Google Patents
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Abstract
A method for utilizing acid gas of a refinery comprises the steps of contacting the acid gas of the refinery containing hydrogen sulfide with an acid medium, then contacting the acid gas with methanol in a reactor heated by molten salt in the presence of a catalyst containing an MFI structure molecular sieve to obtain a mixture containing dimethyl sulfide, and when the conversion rate of methanol is reduced to a condition 1 or the selectivity of dimethyl sulfide is reduced to a condition 2, carrying out the operation of reducing the flow rate of an air flow passing through the molten salt until the conversion rate of methanol is increased to meet a condition 3 and the selectivity of dimethyl sulfide is increased to meet a condition 4. The method can solve the problem of excessive acid gas in a refinery, and has the characteristics of low operation cost and capability of effectively prolonging the one-way service life of the catalyst.
Description
Technical Field
The invention relates to a method for utilizing refinery acid gas, in particular to a method for preparing dimethyl sulfide by utilizing refinery acid gas and methanol.
Background
Hydrogen sulfide is one of the most important sulfur resources in the world, primarily produced during natural gas desulfurization and petroleum processing. The refinery acid gas mainly comes from the processes of acid water stripping, dry gas desulfurization, liquefied gas desulfurization, hydrogenation and the like, and the main component of the refinery acid gas is hydrogen sulfide and also contains a small amount of carbon dioxide, methane, ammonia, water vapor and the like. The demand of petroleum resources in China is rapidly increased, a large amount of high-sulfur crude oil needs to be imported, and the heavy and inferior crude oil generates a large amount of refinery acid gas due to petroleum processing. The hydrogen sulfide gas in the acid gas of the refinery is extremely toxic, inflammable and explosive and can not be directly discharged.
The traditional method of utilizing refinery acid gases is to selectively oxidize the hydrogen sulfide therein to sulfur and water by the claus process. But the price fluctuation of the sulfur product is large, the price is difficult to be increased, and the added value of the product is low. In addition, with the enhancement of environmental regulations, a tail gas treatment device needs to be added in the Claus process to overcome the defect of tail gas pollution, so that the social benefit and the economic benefit of the Claus process are hardly effectively guaranteed.
Dimethyl sulfoxide is an important chemical raw material and is widely applied to the fields of medicines, pesticides, electronic materials, petrochemical industry and carbon fibers. Dimethyl sulfide is an intermediate raw material for synthesizing dimethyl sulfoxide. At present, the dimethyl sulfide is prepared by taking hydrogen sulfide as a raw material, so that the added value is high, and the hydrogen sulfide resource can be effectively utilized.
CN1486786A discloses a catalyst for synthesizing dimethyl sulfide, which uses active alumina as carrier and alkali metal oxide as active component; the active alumina carrier can be one or a mixture of more of transition alumina such as gamma, delta, kappa, rho, eta and the like. The catalyst can be used for the reaction of hydrogen sulfide and methanol to produce dimethyl sulfide.
CN1217326A discloses a method for preparing dimethyl sulfide and methyl mercaptan, wherein a sulfur compound containing 30-99mol% of hydrogen sulfide and methanol are used as raw materials, and the ratio of sulfur in the sulfur compound containing 30-99mol% of hydrogen sulfide: methanol =1:0.6-2.5 (mol ratio), gasifying and preheating to 300 ℃, and then introducing gamma-Al 2 O 3 In a reactor of the catalyst, the reaction temperature is 350-420 ℃, the retention time is 1.5-5 seconds, gas generated by the reaction is cooled by brine ice at minus 18 ℃ to obtain condensed liquid, the condensed liquid is stood for 10-20 minutes and then layered, water at the lower layer is removed, the mixture of dimethyl sulfide and methyl mercaptan at the upper layer is rectified and separated, the fraction at 2.5-5.1 ℃ is intercepted to be methyl mercaptan, and the fraction at 37-39 ℃ is intercepted to be dimethyl sulfide.
US4302605 discloses a process for preparing C 1 -C 12 A continuous gas-phase process for dialkyl sulfides, which comprises reacting C in the presence of a zeolite catalyst 1 -C 12 The alcohol and hydrogen sulfide are reacted at elevated temperatures. The opening of the zeolite catalyst is 7-10 angstrom, the zeolite catalyst is X-type, Y-type or L-type, and Na is used 2 Calculated as O, the alkali metal content is less than 10 wt%; the temperature of the reaction is usually 250 to 450 ℃. The methanol obtained by the method has low conversion rate.
Disclosure of Invention
The invention aims to provide a method for synthesizing dimethyl sulfide by reacting refinery acid gas and methanol, which has the advantages of simple process and low cost, and greatly prolongs the service life of a catalyst.
In order to achieve the above object, the present invention provides a utilization millA process for producing a refinery acid gas, characterized in that it comprises a step of contacting a refinery acid gas containing hydrogen sulfide with an acid medium, and then with methanol in the presence of a catalyst comprising an MFI-structure molecular sieve in a reactor heated with molten salt to obtain a mixture containing dimethyl sulfide, and a step of reducing the flow rate of an air stream passing through the molten salt when the methanol conversion rate is reduced to a condition 1 or the selectivity for dimethyl sulfide is reduced to a condition 2 until the methanol conversion rate is increased to satisfy a condition 3 and the selectivity for dimethyl sulfide is increased to satisfy a condition 4, wherein the refinery acid gas containing hydrogen sulfide and an acid medium are mixed in a ratio of 100 to 3000L as a refinery acid gas: 1L of acidic medium; the condition 1 is that: methanol conversion C and initial methanol conversion C 0 Ratio of C: C 0 0.85 to 0.95, and the condition 2: dimethyl sulfide selectivity S and initial dimethyl sulfide selectivity S 0 Ratio S: S 0 0.85 to 0.95, and the condition 3: methanol conversion C and initial methanol conversion C 0 Ratio of C: C 0 0.9 to 1, and the condition 4: dimethyl sulfide selectivity S and initial dimethyl sulfide selectivity S 0 Ratio of S to S 0 0.9 to 1; the ratio of the condition 1 is smaller than the ratio of the condition 3 and the difference between the ratios is at least 0.01, and the ratio of the condition 2 is smaller than the ratio of the condition 4 and the difference between the ratios is at least 0.01.
The method for utilizing the refinery acid gas is used for preparing the dimethyl sulfide which is a product with high added value and contains sulfur, solves the problem of excessive refinery acid gas, takes the dimethyl sulfide as a raw material to prepare the dimethyl sulfide, and further prepares the dimethyl sulfoxide through oxidation of the dimethyl sulfide, so that the refinery acid gas can be effectively utilized, and the economic benefit of a refinery is improved; in addition, the method is simple and easy to implement, can reduce the operation cost of the device, effectively prolong the one-way service life of the catalyst, reduce the regeneration frequency of the catalyst, and is beneficial to the long-period continuous operation of the reaction device, so that the conversion rate of methanol and the selectivity of dimethyl sulfide are stabilized at the required level.
Detailed Description
According to the invention, the refinery acid gas is a mixed gas containing hydrogen sulfide, and the mixed gas also contains a small amount of ammonia gas, methane, carbon dioxide and water vapor, wherein the molar content of the hydrogen sulfide is more than 90%.
According to the invention, the acidic medium contains one or two of sulfuric acid, phosphoric acid, diammonium hydrogen phosphate and ammonium dihydrogen phosphate solution. Wherein the concentration of the sulfuric acid, the phosphoric acid, the diammonium hydrogen phosphate and the ammonium dihydrogen phosphate solution is 1-4mol/L. More preferably, the concentration of the solution of sulfuric acid, phosphoric acid, diammonium hydrogen phosphate and monoammonium phosphate is 2-3mol/L. In the invention, the acidic medium can effectively absorb the impurity ammonia in the acid gas of the refinery, and the ammonia is prevented from being adsorbed on the surface acid center of the catalyst containing the MFI structure molecular sieve, so that the conversion rate of hydrogen sulfide and the selectivity of dimethyl sulfide in the reaction can be improved. The refinery acid gas containing hydrogen sulfide and the acid medium are mixed according to the following ratio of 100-3000L (standard state, temperature 273.15K, pressure 101.3 kPa) acid gas: 1L of an acidic medium.
In the invention, the reactor for contacting the refinery acid gas and the methanol adopts a molten salt heating mode to provide heat required by the reaction. Possible ways are, for example, to place the reactor in a molten salt heater, in which the molten salt is stirred to generate the heat required for the reaction, and to introduce air through the bottom and to adjust the flow of air to control the increase or decrease of the heat. The molten salt heater can be a sleeve type, heating rods are distributed in the heater, the molten salt in the heater can be one or more of potassium nitrate, sodium nitrate and sodium nitrite, and the initial flow rate of air is 0.01-200NL/min.
According to the invention, the MFI structure molecular sieve has a silica to alumina molar ratio (SiO;) 2 /Al 2 O 3 The same applies hereinafter) can be selected within a wide range. Preferably, the MFI structure molecular sieve has a silica to alumina molar ratio, calculated as the oxide, of from 12 to 200; preferably, the MFI structure molecular sieve has a silica to alumina molar ratio, on an oxide basis, of from 15 to 150; still more preferably, the MFI structure molecular sieve has a silica to alumina mole ratio, calculated as the oxide, of from 20 to 70. When the MFI structure molecular sieve is in the preferred silicon-aluminum molar ratio range, better catalysis can be obtainedThe catalyst can still keep higher catalytic activity in long-period operation of the reaction of hydrogen sulfide and methanol, and higher hydrogen sulfide conversion rate and dimethyl sulfide selectivity are obtained.
According to the invention, the sodium ion content in the molecular sieve with MFI structure is different, which can affect the performance of the molecular sieve with MFI structure. Preferably, na in the molecular sieve of MFI structure is taken as the basis of the total weight of the molecular sieve of MFI structure 2 The content of O is less than or equal to 0.1 weight percent; na in the molecular sieve with MFI structure is preferable 2 The content of O is less than or equal to 0.05 weight percent.
According to the invention, the catalyst containing the MFI structure molecular sieve can optionally be subjected to a steam treatment step before the reaction. The catalyst containing the MFI structure molecular sieve is subjected to steam treatment, so that the hydrothermal stability of the catalyst can be improved, and the selectivity of dimethyl sulfide is further improved. The conditions and the specific mode of operation of the steam treatment are known to those skilled in the art. Preferably, the method of the present invention further comprises, before the reaction, subjecting the catalyst containing the MFI structure molecular sieve to steam treatment at a temperature of 150 to 500 ℃ for 1 to 15 hours, more preferably at a temperature of 200 to 400 ℃ for 1 to 10 hours.
According to the invention, the MFI structure molecular sieve is preferably an HZSM-5 molecular sieve. The HZSM-5 molecular sieve may be obtained by various methods, for example, commercially available, or may be obtained by various methods known in the art. Preferably, the HZSM-5 molecular sieve firstly can adopt a hydrothermal synthesis method to obtain a sodium type ZSM-5 molecular sieve, then sodium ions in the sodium type ZSM-5 molecular sieve are exchanged for ammonium ions through an exchange reaction to form an ammonium type ZSM-5 molecular sieve, and the HZSM-5 molecular sieve is obtained through roasting.
In the invention, the sodium type ZSM-5 molecular sieve is converted into the HZSM-5 molecular sieve by exchange reaction and roasting, and the conventional technical means in the field can be adopted. For example, ammonium salts such as NH may be used 4 Soluble ammonium salts such as Cl, ammonium sulfate and ammonium nitrate are dissolved in deionized water and then mixed with sodium type ZSM-5, stirring the molecular sieve at 60-90 ℃ for 1-4 hours, then filtering, washing, drying at 70-120 ℃, and roasting; wherein the roasting temperature is 450-650 ℃, the roasting time is 1-6 hours, the preferred roasting temperature is 500-600 ℃, and the roasting time is 2-4 hours, thus obtaining the HZSM-5 molecular sieve. The weight ratio of the sodium type ZSM-5 molecular sieve to the ammonium salt is 1:0.2-1, wherein the weight ratio of the sodium type ZSM-5 molecular sieve to the deionized water is 1:4-10.
According to the invention, the content of the molecular sieve of the MFI structure is 20 to 100 wt.%, based on the total amount of the catalyst. In the catalyst, preferably, the content of the molecular sieve of the MFI structure is 50 to 100 wt% based on the total amount of the catalyst, and the content of the molecular sieve of the MFI structure is within the above range, the method provided by the present invention can achieve higher methanol conversion rate and dimethyl sulfide selectivity.
The selection of the support and binder according to the invention is well known to the person skilled in the art, for example the support may be selected from one or more of alumina, silica gel, kaolin, bentonite, diatomaceous earth, natural pumice and expanded perlite. The binder may be selected from one or more of pseudo-boehmite, alumina sol and silica sol.
According to the invention, after the refinery acid gas containing hydrogen sulfide is contacted with an acid medium, the acid gas and methanol can be respectively added into a reactor and contacted on a catalyst containing an MFI structure molecular sieve to carry out synthetic reaction to generate dimethyl sulfide. Preferably, the molar ratio of hydrogen sulfide to methanol is 1:1-4; preferably, the molar ratio of hydrogen sulfide to methanol is 1:2-3. According to the chemical reaction formula, 1 mol of hydrogen sulfide consumes 2mol of methanol to be fed, dimethyl sulfide is synthesized by reaction, and the generation of byproducts can be reduced.
According to the invention, the contacting of the refinery acid gas containing hydrogen sulphide with an acidic medium is carried out in an absorber containing an acidic medium. The absorber containing the acidic medium is at least two absorbers which are used in series and/or in parallel and are switched by a valve. Taking two absorbers as an example, they are used in series and/or in parallel. The two absorbers are named absorber 1 and absorber 2, respectively. Wherein, when the selectivity of dimethyl sulfide in the reaction is reduced to below 85 percent, the acidic medium needs to be replaced. There may be adopted a method of, for example, switching the absorber 1 to a single use state, replacing the acidic medium in the absorber 2, and then replacing the acidic medium in the absorber 1 in the same manner. In order to ensure that the acid gas of the refinery is fully contacted with the acid medium in the absorber, a gas distributor is arranged in the absorber, and the acid medium is stirred by mechanical stirring or magnetic stirring. The gas distributor can adopt a conventional corrosion-resistant gas distributor sold in the market, and the requirement that the acid gas can be uniformly contacted with an acid medium is met. The stirring paddle for mechanical stirring and magnetic stirring can be in the shape of a paddle, an anchor, a turbine, a frame and other conventional stirring paddles, and can be designed into one or more layers of stirring paddles according to requirements.
According to the present invention, the air flow rate of the molten salt heater is reduced when the methanol conversion and dimethyl sulfide selectivity decrease for a period of time during which the reaction is carried out. That is, when the methanol conversion rate is decreased to condition 1 or the dimethyl sulfide selectivity is decreased to condition 2, the air stream for molten salt heating is subjected to an operation of decreasing the flow rate until the methanol conversion rate is increased to satisfy condition 3 and the dimethyl sulfide selectivity is increased to satisfy condition 4; the condition 1 is that: methanol conversion C and initial methanol conversion C 0 Ratio of C to C 0 Is 0.85 to 0.95, and the condition 2: dimethyl sulfide selectivity S and initial dimethyl sulfide selectivity S 0 Ratio of S to S 0 0.85 to 0.95, and the condition 3: methanol conversion C and initial methanol conversion C 0 Ratio of C: C 0 0.9 to 1, and the condition 4: dimethyl sulfide selectivity S and initial dimethyl sulfide selectivity S 0 Ratio S: S 0 0.9 to 1; the ratio described in the condition 1 is smaller than the ratio described in the condition 3 by at least 0.01, preferably at least 0.03, and more preferably at least 0.05, and the ratio described in the condition 2 is smaller than the ratio described in the condition 4 by at least 0.01, preferably at least 0.03, and more preferably at least 0.05.
According to the present invention, in the operation of reducing the flow rate of the air flow for molten salt heating, any means of adjusting the air flow rate that can achieve the object of the conditions 3 and 4 may be used, and the flow rate of the air may be reduced, for example, in the range of 0.01 to 1NL/min, preferably 0.1 to 0.8 NL/min.
In the invention, the reaction process of the catalyst for catalyzing the reaction of the hydrogen sulfide and the methanol is a gas-solid catalytic reaction process. Reactors suitable for gas-solid catalytic reaction processes in the art may be used, for example, fixed bed reactors, such as tubular reactors, may be used. The catalyst is filled in the tubular reactor to form a catalyst bed. The tubular reactor is heated by a molten salt heating mode, so that the temperature of the catalyst bed layer reaches the reaction temperature. The refinery acid gas containing hydrogen sulfide and methanol after being contacted with an acid medium are introduced from one end of the tubular reactor to be contacted with the catalyst bed layer for reaction, and reaction products are collected at the other end of the tubular reactor.
In the reaction of hydrogen sulfide and methanol to dimethyl sulfide according to the present invention, the total amount of reactants hydrogen sulfide and methanol fed to the reactor is calculated as the space velocity of the total gas volume, wherein hydrogen sulfide is fed in gaseous form and methanol is fed in liquid form but converted to the volume of gas at the reaction temperature when calculating the amount passing through the catalyst bed. Preferably, the total gas volume space velocity of the hydrogen sulfide and the methanol is 200-2000h -1 Preferably, the total gas volume space velocity of the hydrogen sulfide and the methanol is 500-1500h -1 . The gas volume space velocity refers to the total gas volume of hydrogen sulfide and methanol passing per unit volume of catalyst per unit time (hour).
According to the present invention, preferably, the conditions of the catalytic reaction include: the reaction temperature is 250-500 deg.C, and the reaction pressure is 1-10atm. It is preferable that the reaction temperature is 270 to 380 ℃ and the reaction pressure is 1 to 5atm in terms of gauge pressure. The temperature of the reaction is the temperature of the catalyst bed layer in the reactor, and the pressure of the reaction is the pressure in the reactor.
The present invention will be described in detail below by way of examples, but the present invention is not limited thereto.
In the examples, the contents of the components of the reaction product were measured by gas chromatography (gas chromatograph model agilent 7890, inorganic components were measured by TCD detector, organic components were measured by FID detector); the molar ratio of Si to Al of the molecular sieve was measured by X-ray fluorescence (X-ray fluorescence spectrometer 3013, manufactured by Nippon Denshi electric motors Co., ltd., tungsten target, excitation voltage 40kV, and excitation current 50 mA).
In the following examples and comparative examples, the contents of the respective components in the reaction product were obtained by gas chromatography analysis, and on the basis of the contents, the methanol conversion and the dimethyl sulfide selectivity were calculated by the following formulas:
C methanol ＝[(M 0 Methanol –M Methanol )/M 0 Methanol ]*100％
In the above formula, C Methanol Representing the methanol conversion;
M 0 methanol Represents the feeding amount of methanol in the reaction;
M methanol Represents the amount of methanol in the reaction product;
S dimethyl sulfide ＝[2*M Dimethyl sulfide /(M 0 Methanol *C Methanol ]*100％
In the above formula, S Dimethyl sulfide Represents a dimethyl sulfide selectivity;
M dimethyl sulfide Represents the amount of dimethyl sulfide in the reaction product;
M 0 methanol Represents the feeding amount of methanol in the reaction;
C methanol Representing the methanol conversion;
example 1
This example illustrates the process of this invention for the production of dimethyl sulfide from refinery acid gases.
HZSM-5 is used as an active phase, kaolin is used as a carrier, pseudo-boehmite is used as a binder to prepare the catalyst, the silica-alumina ratio of the HZSM-5 is 41.8, the content of sodium oxide is 0.02 wt%, and the weight content of the molecular sieve is 80% based on the total weight of the catalyst. Adding 200g of HZSM-5 molecular sieve into deionized water, performing ultrasonic dispersion for 50min, and adding 40g of pseudothin water into the slurryThe ultrasonic dispersion of the aluminum and 10g of kaolin is continued for 30min. And (4) carrying out suction filtration on the mixed slurry, and drying the obtained filter cake in a vacuum oven at the baking temperature of 45 ℃. Putting the dried filter cake into a strip extruding machine, kneading the filter cake into a cluster by using a nitric acid aqueous solution, extruding the cluster into strips and forming, wherein the catalyst is cylindrical and has the diameter of 2mm. The formed catalyst is placed in a reaction tube and treated by 35 percent ethanol water solution by mass percent for 8 hours at 170 ℃, and the liquid weight hourly space velocity is 0.05 hour -1 。
The reaction of acid gas and methanol in refinery is carried out in a fixed bed tubular reactor, the shaped catalyst is loaded in a tubular reactor with the diameter of 2.8cm and the length of 140cm, the volume of the catalyst particle bed layer is 100cm 3 . The catalyst was treated with steam at 220 ℃ for 4h before the reaction. Before entering a reactor, the acid gas of the refinery is firstly passed through 2 acid medium absorbers filled with ammonium dihydrogen phosphate, the concentration of the ammonium dihydrogen phosphate is 2.4mol/L, and the 2 absorbers are connected in series. The tubular reactor is placed in a molten salt heater, 55% of potassium nitrate and 45% of sodium nitrate molten salt are filled in the molten salt heater, and the initial flow of air introduced into the bottom of the molten salt heater is 40NL/min.
The molar content of hydrogen sulfide in acid gas of a refinery used in the reaction is 92.7%, the reaction temperature is set to be 370 ℃, the reaction pressure is 1atm, the feeding molar ratio of hydrogen sulfide to methanol is 1 -1 Under the conditions of (1), a reaction for preparing dimethyl sulfide is carried out. And continuously analyzing the reaction products by using a gas chromatograph in the reaction process, and calculating the methanol conversion rate and the dimethyl sulfide selectivity according to the analysis result.
With methanol conversion and dimethyl sulfide selectivity of reaction 1h as C for the start of the reaction 0 And S 0 98.7% and 96.4%, respectively, are listed in Table 1. When the methanol conversion rate C in the reaction is equal to the initial methanol conversion rate C of the reaction 0 Ratio of C to C 0 0.87, in which the flow rate of air in the molten salt heating furnace was reduced at a rate of 0.8NL/min per day, and the methanol conversion C was compared with the initial methanol conversion C when the flow rate of air in the molten salt heating furnace was 33.6NL/min 0 Ratio of C: C 0 Returned to 0.92 and dimethylsulfide selectivity S to initial dimethylsulfideEther selectivity S 0 Ratio of S to S 0 The temperature is recovered to 0.91, and the air flow in the molten salt heating furnace is kept; when C: C 0 When the flow rate of the air in the molten salt heating furnace is reduced to 0.87 again, the flow rate of the air in the molten salt heating furnace is reduced at a rate of 0.8NL/min per day, and when the flow rate of the air is 25.6NL/min, the methanol conversion rate C is equal to the initial methanol conversion rate C 0 Ratio of C: C 0 Is restored to 0.92 and the selectivity S of dimethyl sulfide and the selectivity S of the initial dimethyl sulfide 0 Ratio S: S 0 The temperature is recovered to 0.91, and the air flow in the molten salt heating furnace is kept; the above operations were repeated a plurality of times, and when the reaction was carried out for 1000 hours, the flow rate of air was 16.0NL/min, and the methanol conversion and the selectivity for dimethyl sulfide were as shown in Table 1.
Example 2
This example illustrates the process of this invention for the production of dimethyl sulfide from refinery acid gases.
HZSM-5 is used as an active phase, alumina is used as a carrier, pseudo-boehmite is used as a binder to prepare the catalyst, the silica-alumina ratio of the HZSM-5 is 31.7, the content of sodium oxide is 0.03 weight percent, and the weight content of the molecular sieve is 70 percent based on the total weight of the catalyst. Adding 200g of HZSM-5 molecular sieve into deionized water, performing ultrasonic dispersion for 50min, adding 60g of pseudo-boehmite and 25.6g of alumina into the slurry, and continuing to perform ultrasonic dispersion for 30min. And (4) carrying out suction filtration on the mixed slurry, and drying the obtained filter cake in a vacuum oven at the baking temperature of 40 ℃. Putting the dried filter cake into a strip extruding machine, kneading the filter cake into a cluster by using a nitric acid aqueous solution, extruding the cluster into strips and forming, wherein the catalyst is cylindrical and has the diameter of 2mm. Placing the formed catalyst in a reaction tube, treating with 50% ethanol water solution at 200 deg.C for 7h, and liquid weight hourly space velocity of 0.04h -1 。
The reaction of acid gas and methanol in refinery is carried out in a fixed bed tubular reactor, the shaped catalyst is loaded in a tubular reactor with the diameter of 2.8cm and the length of 140cm, the volume of the catalyst particle bed layer is 100cm 3 . The catalyst was treated with steam at 300 ℃ for 2h before the reaction. Before entering a reactor, refinery acid gas passes through 2 acid medium absorbers filled with dilute sulfuric acid, the concentration of the sulfuric acid is 2.8mol/L, and the 2 absorbers are connected in the way thatAre connected in parallel. The tubular reactor is arranged in a molten salt heater, 55% of sodium nitrate and 45% of sodium nitrite molten salt are filled in the molten salt heater, and the initial flow of air introduced into the bottom of the molten salt heater is 35NL/min.
The molar content of hydrogen sulfide in acid gas of a refinery used in the reaction is 93.5%, the reaction temperature is set to be 350 ℃, the reaction pressure is 1atm, the feeding molar ratio of hydrogen sulfide to methanol is 1 -1 Under the conditions of (1), a reaction for preparing dimethyl sulfide is carried out. And continuously analyzing the reaction products by using a gas chromatograph in the reaction process, and calculating the methanol conversion rate and the dimethyl sulfide selectivity according to the analysis result.
With methanol conversion and dimethyl sulfide selectivity of reaction 1h as C for the start of the reaction 0 And S 0 Listed in table 1. When the selectivity S of dimethyl sulfide in the reaction is equal to the selectivity S of dimethyl sulfide in the initial reaction 0 Ratio S: S 0 0.86, in which the flow rate of air in the molten salt heating furnace was decreased at a rate of 0.5NL/min per day, and when the flow rate of air in the molten salt heating furnace was 29.5NL/min, the methanol conversion C was compared with the initial methanol conversion C 0 Ratio of C to C 0 Is restored to 0.93 and the selectivity S for dimethyl sulfide and the selectivity S for the initial dimethyl sulfide 0 Ratio of S to S 0 The air flow rate is restored to 0.92, and the air flow rate in the molten salt heating furnace is maintained; when C: C 0 When the flow rate of the air in the molten salt heating furnace is again 0.86, the flow rate of the air in the molten salt heating furnace is reduced at a rate of 0.5NL/min per day, and when the flow rate of the air is 22.5NL/min, the methanol conversion C is equal to the initial methanol conversion C 0 Ratio of C: C 0 Returned to 0.93 and the dimethyl sulfide selectivity S and the initial dimethyl sulfide selectivity S 0 Ratio S: S 0 The air flow rate is restored to 0.92, and the air flow rate in the molten salt heating furnace is maintained; the above operations were repeated a plurality of times, and when the reaction was carried out for 1200 hours, the flow rate of air was 18.5NL/min, and the methanol conversion and the selectivity for dimethyl sulfide were as shown in Table 1.
Example 3
This example illustrates the process of this invention for the preparation of dimethyl sulfide using refinery acid gases.
HZSM-5 is used as an active phase, pseudo-boehmite and alumina sol are used as binders to prepare the catalyst, the silicon-aluminum ratio of HZSM-5 is 52.5, the content of sodium oxide is 0.02 percent by weight, and the content of the molecular sieve is 90 percent by weight based on the total amount of the catalyst. 200g of HZSM-5 molecular sieve is added into deionized water, ultrasonic dispersion is carried out for 60min, then 20g of pseudo-boehmite is added into the slurry, and the ultrasonic dispersion is continued for 40min. And (4) carrying out suction filtration on the mixed slurry, and drying the obtained filter cake in a vacuum oven at the baking temperature of 40 ℃. And putting the dried filter cake into a strip extruding machine, adding 11g of alumina sol, kneading into a cluster by using a nitric acid aqueous solution, extruding and forming, wherein the catalyst is cylindrical and has the diameter of 2mm. The formed catalyst is placed in a reaction tube and treated by 40 percent ethanol water solution by mass percent for 8 hours at 180 ℃, and the liquid weight hourly space velocity is 0.04 hour -1 。
The reaction of acid gas and methanol in refinery is carried out in a fixed bed tubular reactor, the shaped catalyst is loaded in a tubular reactor with the diameter of 2.8cm and the length of 140cm, the volume of the catalyst particle bed layer is 100cm 3 . The catalyst was treated with steam at 290 ℃ for 4h before the reaction. Before entering a reactor, refinery acid gas passes through 2 acid medium absorbers filled with dilute sulfuric acid, the concentration of a sulfuric acid solution is 2mol/L, and the 2 absorbers are connected in series. The tubular reactor is arranged in a molten salt heater, 55 percent of sodium nitrate and 45 percent of sodium nitrite molten salt are filled in the molten salt heater, and the initial flow of air introduced into the bottom of the molten salt heater is 38NL/min.
The molar content of hydrogen sulfide in acid gas of a refinery used in the reaction is 95.0 percent, the reaction temperature is set to be 340 ℃, the reaction pressure is set to be 1atm, the feeding molar ratio of the hydrogen sulfide to the methanol is 1atm, and the total gas volume space velocity is 550h -1 Under the conditions of (1), a reaction for preparing dimethyl sulfide is carried out. And continuously analyzing the reaction products by using a gas chromatograph in the reaction process, and calculating the methanol conversion rate and the dimethyl sulfide selectivity according to the analysis result.
With the methanol conversion and dimethyl sulfide selectivity of the reaction 1h as the initial C of the reaction 0 And S 0 Listed in table 1. When the methanol conversion rate C in the reaction is equal to the initial methanol conversion rate C of the reaction 0 Ratio of C: C 0 0.85, when the flow rate of air in the molten salt heating furnace was decreased at a rate of 0.4NL/min per day, the methanol conversion C was compared with the initial methanol conversion C when the flow rate of air in the molten salt heating furnace was 34.4NL/min 0 Ratio of C to C 0 Returned to 0.92 and the selectivity S to dimethylsulfide and the selectivity S to initial dimethylsulfide 0 Ratio S: S 0 The flow rate is returned to 0.92, and the air flow in the molten salt heating furnace is maintained; when C: C 0 When the flow rate of the air in the molten salt heating furnace is again 0.85, the flow rate of the air in the molten salt heating furnace is reduced at a rate of 0.4NL/min per day, and when the flow rate of the air is 29.2NL/min, the methanol conversion C is equal to the initial methanol conversion C 0 Ratio of C: C 0 Is restored to 0.92 and the selectivity S of dimethyl sulfide and the selectivity S of the initial dimethyl sulfide 0 Ratio S: S 0 The air flow rate is restored to 0.92, and the air flow rate in the molten salt heating furnace is maintained; the above operation was repeated several times, and when the reaction was carried out for 1400 hours, the flow rate of air was 19.6NL/min, and the methanol conversion and the selectivity for dimethyl sulfide were as shown in Table 1.
Example 4
This example illustrates the process of this invention for the production of dimethyl sulfide from refinery acid gases.
HZSM-5 is used as an active phase, silica gel is used as a carrier, pseudo-boehmite is used as a binder to prepare the catalyst, the silica-alumina ratio of the HZSM-5 is 29.3, the content of sodium oxide is 0.04 wt%, and the weight content of the molecular sieve is 70% based on the total amount of the catalyst. 200g of HZSM-5 molecular sieve is added into deionized water, ultrasonic dispersion is carried out for 50min, 70g of pseudo-boehmite and 15.6g of silica gel are added into the slurry, and the ultrasonic dispersion is continued for 40min. And (4) carrying out suction filtration on the mixed slurry, and drying the obtained filter cake in a vacuum oven at the baking temperature of 40 ℃. Putting the dried filter cake into a strip extruding machine, kneading the filter cake into a cluster by using a nitric acid aqueous solution, extruding the cluster for molding, wherein the catalyst is cylindrical and has the diameter of 2mm. Placing the formed catalyst in a reaction tube, treating with 30% ethanol water solution at 180 deg.C for 8h, and liquid weight hourly space velocity of 0.04h -1 。
The reaction of acid gas and methanol in refinery is carried out in a fixed bed tubular reactor, and the shaped catalyst is packed in a tubular reactor with diameter of 2.8cm and lengthIn a tubular reactor with a temperature of 140cm, the bed volume of the catalyst particles is 100cm 3 . The catalyst was treated with steam at 200 ℃ for 5h before the reaction. Before entering a reactor, the acid gas of the refinery is firstly passed through 2 acid medium absorbers filled with ammonium dihydrogen phosphate, the concentration of the ammonium dihydrogen phosphate solution is 3mol/L, and the 2 absorbers are connected in parallel. The tubular reactor is arranged in a molten salt heater, 55 percent of sodium nitrate and 45 percent of sodium nitrite molten salt are filled in the molten salt heater, and the initial flow of air introduced into the bottom of the molten salt heater is 30NL/min.
The molar content of hydrogen sulfide in acid gas of a refinery used in the reaction is 92.9%, the reaction temperature is set to be 330 ℃, the reaction pressure is set to be 1atm, the feeding molar ratio of hydrogen sulfide to methanol is 1atm, and the total gas volume space velocity is 600h -1 Under the conditions of (3), a reaction for preparing dimethyl sulfide is carried out. And continuously analyzing the reaction products by using a gas chromatograph in the reaction process, and calculating the methanol conversion rate and the dimethyl sulfide selectivity according to the analysis result.
With the methanol conversion and dimethyl sulfide selectivity of the reaction 1h as the initial C of the reaction 0 And S 0 Listed in table 1. When the selectivity S of dimethyl sulfide in the reaction is equal to the selectivity S of dimethyl sulfide in the initial reaction 0 Ratio S: S 0 0.85, when the flow rate of air in the molten salt heating furnace was decreased at a rate of 0.4NL/min per day, the methanol conversion C was compared with the initial methanol conversion C when the flow rate of air in the molten salt heating furnace was 25.6NL/min 0 Ratio of C: C 0 Is restored to 0.94 and the selectivity S of dimethyl sulfide and the selectivity S of the initial dimethyl sulfide 0 Ratio S: S 0 The air flow rate is restored to 0.92, and the air flow rate in the molten salt heating furnace is maintained; when C: C 0 When the flow rate of the air in the molten salt heating furnace is again 0.85, the flow rate of the air in the molten salt heating furnace is reduced at a rate of 0.4NL/min per day, and when the flow rate of the air is 220.0NL/min, the methanol conversion rate C is equal to the initial methanol conversion rate C 0 Ratio of C: C 0 Returned to 0.94 and the selectivity S for dimethyl sulfide and the selectivity S for initial dimethyl sulfide 0 Ratio S: S 0 The air flow rate is restored to 0.92, and the air flow rate in the molten salt heating furnace is maintained; repeating the above operations for a plurality of times whenThe reaction was carried out for 1300h with an air flow of 14.0NL/min, the methanol conversion and the selectivity for dimethyl sulfide are given in Table 1.
Example 5
This example illustrates the process of this invention for the production of dimethyl sulfide from refinery acid gases.
HZSM-5 is used as an active phase, alumina is used as a carrier, pseudo-boehmite is used as a binder to prepare the catalyst, the silica-alumina ratio of the HZSM-5 is 49.5, the sodium oxide content is 0.01 wt%, and the molecular sieve weight content is 80% based on the total amount of the catalyst. 200g of HZSM-5 molecular sieve is added into deionized water, ultrasonic dispersion is carried out for 50min, then 40g of pseudo-boehmite and 10g of alumina are added into the slurry, and the ultrasonic dispersion is continued for 40min. And (4) carrying out suction filtration on the mixed slurry, and drying the obtained filter cake in a vacuum oven at the baking temperature of 50 ℃. Putting the dried filter cake into a strip extruding machine, kneading the filter cake into a cluster by using a nitric acid aqueous solution, extruding the cluster into strips and forming, wherein the catalyst is cylindrical and has the diameter of 2mm. The formed catalyst is placed in a reaction tube and treated with 40 percent ethanol water solution by mass percent for 4 hours at 210 ℃, and the liquid weight hourly space velocity is 0.03 hour -1 。
The reaction of refinery acid gas and methanol is carried out in a fixed bed tubular reactor, the formed catalyst is filled in a tubular reactor with the diameter of 2.8cm and the length of 140cm, and the volume of a catalyst particle bed layer is 100cm 3 . The catalyst was treated with steam at 340 ℃ for 1h before the reaction. Before entering a reactor, the acid gas of the refinery first passes through 2 acid medium absorbers filled with mixed liquid of diammonium hydrogen phosphate and ammonium dihydrogen phosphate, the concentration of the mixed acid liquid is 4mol/L, and the 2 absorbers are connected in series. The tubular reactor is arranged in a molten salt heater, 55% of potassium nitrate and 45% of sodium nitrite molten salt are filled in the molten salt heater, and the initial flow of air introduced into the bottom of the molten salt heater is 37NL/min.
The molar content of hydrogen sulfide in acid gas of a refinery used in the reaction is 95.6%, the reaction temperature is set to be 350 ℃, the reaction pressure is 1atm, the feeding molar ratio of hydrogen sulfide to methanol is 1 -1 Under the conditions of (1), a reaction for preparing dimethyl sulfide is carried out. The reaction process is continuously performed by a gas chromatographThe products of the reaction were analyzed, and the methanol conversion and dimethyl sulfide selectivity were calculated from the analysis results.
With the methanol conversion and dimethyl sulfide selectivity of the reaction 1h as the initial C of the reaction 0 And S 0 Listed in table 1. When the methanol conversion rate C in the reaction is equal to the initial methanol conversion rate C of the reaction 0 Ratio of C: C 0 0.86, in which the flow rate of air in the molten salt heating furnace was reduced at a rate of 0.5NL/min per day, and the methanol conversion C was compared with the initial methanol conversion C when the flow rate of air in the molten salt heating furnace was 32.0NL/min 0 Ratio of C: C 0 Is restored to 0.93 and the selectivity S for dimethyl sulfide and the selectivity S for the initial dimethyl sulfide 0 Ratio of S to S 0 The temperature is recovered to 0.91, and the air flow in the molten salt heating furnace is kept; when C: C 0 When the flow rate of the air in the molten salt heating furnace is again 0.86, the flow rate of the air in the molten salt heating furnace is reduced at a rate of 0.5NL/min per day, and when the flow rate of the air is 25.5NL/min, the methanol conversion C is equal to the initial methanol conversion C 0 Ratio of C: C 0 Returned to 0.93 and the dimethyl sulfide selectivity S and the initial dimethyl sulfide selectivity S 0 Ratio S: S 0 The flow rate is returned to 0.91, and the air flow in the molten salt heating furnace is kept; the above operation was repeated several times, and when the reaction was carried out for 1300 hours, the flow rate of air was 17.5NL/min, and the methanol conversion and the selectivity for dimethyl sulfide were as shown in Table 1.
Example 6
This example illustrates the process of this invention for the preparation of dimethyl sulfide using refinery acid gases.
HZSM-5 is used as an active phase, kaolin is used as a carrier, pseudo-boehmite and alumina sol are used as binders to prepare the catalyst, the silica-alumina ratio of the HZSM-5 is 58.6, the content of sodium oxide is 0.02 percent by weight, and the weight content of the molecular sieve is 70 percent by taking the total weight of the catalyst as a reference. Adding 200g of HZSM-5 molecular sieve into deionized water, performing ultrasonic dispersion for 60min, adding 60g of pseudo-boehmite and 20g of kaolin into the slurry, and continuing to perform ultrasonic dispersion for 60min. And (4) carrying out suction filtration on the mixed slurry, and drying the obtained filter cake in a vacuum oven at the baking temperature of 50 ℃. Putting the dried filter cake into a strip extruding machine, adding 28g of alumina sol, and adding nitric acidKneading the aqueous solution into a cluster, extruding the cluster into strips, and forming the catalyst into a cylinder with the diameter of 2mm. Placing the formed catalyst in a reaction tube, treating with 50% ethanol water solution at 160 deg.C for 7h, and liquid weight hourly space velocity of 0.04h -1 。
The reaction of acid gas and methanol in refinery is carried out in a fixed bed tubular reactor, the shaped catalyst is loaded in a tubular reactor with the diameter of 2.8cm and the length of 140cm, the volume of the catalyst particle bed layer is 100cm 3 . The catalyst was treated with steam at 250 ℃ for 5h before the reaction. Before entering a reactor, refinery acid gas passes through 2 acid medium absorbers filled with phosphoric acid, the concentration of a phosphoric acid solution is 3mol/L, and the 2 absorbers are connected in series. The tubular reactor is arranged in a molten salt heater, 55 percent of potassium nitrate and 45 percent of sodium nitrite molten salt are filled in the molten salt heater, and the initial flow of air introduced into the bottom of the molten salt heater is 32NL/min.
The molar content of hydrogen sulfide in acid gas of a refinery used in the reaction is 93.9%, the reaction temperature is set to be 390 ℃, the reaction pressure is set to be 1atm, the feeding molar ratio of hydrogen sulfide to methanol is 1atm and 2, and the total gas volume space velocity is 800h -1 Under the conditions of (1), a reaction for preparing dimethyl sulfide is carried out. And continuously analyzing the reaction products by using a gas chromatograph in the reaction process, and calculating the methanol conversion rate and the dimethyl sulfide selectivity according to the analysis result.
With the methanol conversion and dimethyl sulfide selectivity of the reaction 1h as the initial C of the reaction 0 And S 0 Listed in table 1. When the selectivity S of dimethyl sulfide in the reaction is different from the selectivity S of dimethyl sulfide in the initial reaction 0 Ratio of S to S 0 0.87, when the flow rate of air in the molten salt heating furnace was decreased at a rate of 0.4NL/min per day, and when the flow rate of air in the molten salt heating furnace was 27.2NL/min, the methanol conversion C was compared with the initial methanol conversion C 0 Ratio of C: C 0 Is restored to 0.91 and the selectivity S for dimethyl sulfide and the selectivity S for the initial dimethyl sulfide 0 Ratio S: S 0 The flow rate is returned to 0.91, and the air flow in the molten salt heating furnace is kept; when C: C 0 At 0.87 again, the molten salt addition was reduced at a rate of 0.4NL/min per dayThe flow rate of air in the hot furnace, when the flow rate of air was 20.0NL/min, the methanol conversion C was compared with the initial methanol conversion C 0 Ratio of C: C 0 Is restored to 0.91 and the selectivity S for dimethyl sulfide and the selectivity S for the initial dimethyl sulfide 0 Ratio S: S 0 The temperature is recovered to 0.91, and the air flow in the molten salt heating furnace is kept; the above operation was repeated a plurality of times, and when the reaction was carried out for 1500 hours, the flow rate of air was 13.6NL/min, and the methanol conversion and the selectivity for dimethyl sulfide were as shown in Table 1.
Example 7
The procedure of example 1 was followed except that the flow rate of air in the molten salt heating furnace was decreased at a rate of 0.6NL/min per day, the reaction was carried out for 1200 hours, the flow rate of air in the molten salt heating furnace was 19.0NL/min, the conversion of methanol and the selectivity for dimethyl sulfide were continuously monitored during the reaction, and the conversion of methanol and the selectivity for dimethyl sulfide for reactions 1 hour and 1200 hours were as shown in Table 1.
Comparative example 1
The process of example 1 was followed except that the refinery acid gas was not passed through the acid medium absorber containing ammonium dihydrogen phosphate before entering the reaction tube and the air flow in the molten salt-heating furnace was not reduced during the reaction, and the methanol conversion and dimethyl sulfide selectivity for the reactions 1h and 800h were as shown in Table 1.
Comparative example 2
The process of example 2 was followed except that the refinery acid gas was not passed through the sulfuric acid-containing acid medium absorber before entering the reaction tube and the air flow in the molten salt furnace was not reduced during the reaction, and the methanol conversion and dimethyl sulfide selectivity for the reactions 1h and 1000h are shown in Table 1.
TABLE 1
It can be seen from the data in table 1 that, according to the method for preparing dimethyl sulfide by using refinery acid gas provided by the invention, before the refinery acid gas reacts with methanol, the refinery acid gas passes through the absorber filled with an acid medium, and the flow rate of air in the molten salt heating furnace is reduced in the reaction process, so that higher methanol conversion rate and dimethyl sulfide selectivity can be obtained, and the methanol conversion rate of more than 86% and the dimethyl sulfide selectivity of more than 85% can be maintained after 1000-1500 hours of operation, thereby being beneficial to stable long-period operation of the device.
The preferred embodiments of the present invention have been described in detail, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present disclosure, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (29)
1. A method of utilizing refinery acid gas, comprising the steps of contacting a refinery acid gas containing hydrogen sulfide with an acid medium, and then contacting with methanol in a molten salt heated reactor in the presence of a catalyst comprising an MFI structure molecular sieve to obtain a mixture containing dimethyl sulfide, and when the methanol conversion rate decreases to condition 1 or the dimethyl sulfide selectivity decreases to condition 2, subjecting an air stream passing through the molten salt to a flow rate decreasing operation until the methanol conversion rate increases to satisfy condition 3 and the dimethyl sulfide selectivity increases to satisfy condition 4, wherein the refinery acid gas containing hydrogen sulfide and the acid medium are mixed in a ratio of 100 to 3000L of the refinery acid gas: 1L of acidic medium; the condition 1: methanol conversion C and initial methanol conversion C 0 Ratio of C: C 0 0.85 to 0.95, and the condition 2: dimethyl sulfide selectivity S and initial dimethyl sulfide selectivity S 0 Ratio S: S 0 0.85 to 0.95, and the condition 3: methanol conversion C and initial methanol conversion C 0 Ratio of C: C 0 0.9 to 1, and condition 4: dimethyl sulfide selectivity S and initial dimethyl sulfide selectivity S 0 Ratio of S to S 0 0.9 to 1; the ratio of the condition 1 is smaller than the ratio of the condition 3 and the difference between the ratios is at least 0.01, and the ratio of the condition 2 is smaller than the ratio of the condition 4 and the difference between the ratios is at least 0.01.
2. The method of claim 1 wherein said refinery acid gas is a mixed gas containing hydrogen sulfide, said mixed gas further containing small amounts of ammonia, methane, carbon dioxide and steam, wherein the molar content of hydrogen sulfide is greater than 90%.
3. The process of claim 1, wherein the acidic medium is selected from one or more of sulfuric acid, phosphoric acid, diammonium phosphate, and a solution of monoammonium phosphate.
4. The method according to claim 3, wherein the concentration of said sulfuric acid, phosphoric acid, diammonium hydrogen phosphate and ammonium dihydrogen phosphate solution is 1 to 4mol/L.
5. The method according to claim 4, wherein the concentration is 2 to 3mol/L.
6. The process of claim 1 wherein the MFI structure molecular sieve has a silica to alumina molar ratio, on an oxide basis, of from 12 to 200.
7. The process of claim 6 wherein the MFI structure molecular sieve has a silica to alumina mole ratio, on an oxide basis, of from 15 to 150.
8. The process of claim 7 where the MFI structure molecular sieve has a silica to alumina mole ratio, on an oxide basis, of from 20 to 70.
9. The process of claim 1 wherein the molecular sieve of MFI structure contains Na, based on the total weight of the molecular sieve of MFI structure 2 The content of O is less than or equal to 0.1 weight percent.
10. The process according to claim 1, wherein the molecular sieve of the MFI structure is present in an amount of from 20 to 100 wt.%, based on the total amount of the catalyst.
11. The process of claim 1 wherein the catalyst further comprises a support and a binder.
12. The method of claim 11, wherein the support is selected from one or more of alumina, silica gel, kaolin, bentonite, diatomaceous earth, natural pumice, and expanded perlite; the binder is selected from one or more of pseudo-boehmite, aluminum sol and silica sol.
13. The process of any one of claims 1 to 12 further comprising steam treating the catalyst comprising a molecular sieve of MFI structure at a temperature of from 150 ℃ to 500 ℃ for a time of from 1 to 15 hours prior to the reacting.
14. The method according to claim 13, wherein the temperature of the steam treatment is 200-400 ℃ and the time of the steam treatment is 1-10 hours.
15. The process of claim 1 wherein the molecular sieve of the MFI structure is an HZSM-5 molecular sieve.
16. The process according to claim 1, wherein said acidic medium is replaced when the selectivity to dimethyl sulfide in the reaction falls below 85%.
17. The process of claim 1 wherein said contacting of said refinery acid gas containing hydrogen sulfide with an acidic medium is carried out in an absorber and said catalyst comprising a molecular sieve of MFI structure is packed in a fixed bed.
18. The process of claim 17, wherein there are at least two absorbers, which are used in series and/or in parallel.
19. The process according to claim 17, wherein said absorbers are two and are used in series and/or in parallel.
20. The process of claim 17, wherein the absorber is equipped with a gas sparger and has a mechanical or magnetic stirring means to agitate the acidic medium.
21. The method of claim 17, wherein the absorber is a kettle.
22. The method according to claim 1, wherein the molten salt is one or more of potassium nitrate, sodium nitrate and sodium nitrite.
23. The method of claim 1 in which the initial flow rate of the air stream through the molten salt is 0.01-200NL/min.
24. A method according to claim 1, wherein said reducing the flow rate of the air flow through the molten salt is carried out by reducing the flow rate by an amount of 0.01-1 NL/min.
25. The process of claim 1, wherein the total gas volume space velocity of hydrogen sulfide and methanol is from 200 to 2000h -1 Wherein the hydrogen sulfide is fed as a gas and the methanol is fed as a liquid but converted to the volume of gas at the reaction temperature when calculating the amount passed through the catalyst bed.
26. The process of claim 25 wherein the total gas volume space velocity of hydrogen sulfide and methanol is500-1500h -1 。
27. The process of claim 1 wherein the temperature in the reactor is from 250 ℃ to 500 ℃ and the molar ratio of hydrogen sulfide to methanol is from 1:1-4.
28. The method according to claim 1, wherein said ratio of condition 1 is less than said ratio of condition 3 by at least 0.03, and said ratio of condition 2 is less than said ratio of condition 4 by at least 0.03.
29. The method according to claim 1, wherein the ratio of condition 1 is less than the ratio of condition 3 by at least 0.05, and the ratio of condition 2 is less than the ratio of condition 4 by at least 0.05.
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| US4302605A (en) * | 1980-04-18 | 1981-11-24 | Pennwalt Corporation | Process for the manufacture of dimethyl sulfide |
| CN1217326A (en) * | 1998-09-03 | 1999-05-26 | 田锡义 | Process for preparing dimethyl thio-ether and methylthio-alcohol |
| CN1486786A (en) * | 2002-09-30 | 2004-04-07 | 中国石化集团齐鲁石油化工公司 | Catalyst for synthesizing dimethyl thioether and its prepn |
| CN107790173A (en) * | 2016-09-07 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method for the catalyst and synthesizing dimethyl thioether for preparing dimethyl sulfide |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4302605A (en) * | 1980-04-18 | 1981-11-24 | Pennwalt Corporation | Process for the manufacture of dimethyl sulfide |
| CN1217326A (en) * | 1998-09-03 | 1999-05-26 | 田锡义 | Process for preparing dimethyl thio-ether and methylthio-alcohol |
| CN1486786A (en) * | 2002-09-30 | 2004-04-07 | 中国石化集团齐鲁石油化工公司 | Catalyst for synthesizing dimethyl thioether and its prepn |
| CN107790173A (en) * | 2016-09-07 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method for the catalyst and synthesizing dimethyl thioether for preparing dimethyl sulfide |
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