CN102381924B - Method for purifying propylene coarse product containing sulfur-containing compound - Google Patents
Method for purifying propylene coarse product containing sulfur-containing compound Download PDFInfo
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- CN102381924B CN102381924B CN2010102740375A CN201010274037A CN102381924B CN 102381924 B CN102381924 B CN 102381924B CN 2010102740375 A CN2010102740375 A CN 2010102740375A CN 201010274037 A CN201010274037 A CN 201010274037A CN 102381924 B CN102381924 B CN 102381924B
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Abstract
The invention provides a method for purifying a propylene coarse product containing a sulfur-containing compound. The method is characterized by comprising the step of enabling the propylene coarse product containing the sulfur-containing compound to be sequentially contacted with a hydrolytic agent and a desulfurizing agent, wherein the desulfurizing agent contains zinc oxide, sodium carbonate and bonding agent. According to the method provided by the invention, the sulfur-containing compound in the propylene coarse product can be fully removed, and thereby a propylene product with higher purity can be prepared.
Description
Technical field
The present invention relates to a kind of purification process that contains the thick product of propylene of sulfocompound.
Background technology
Usually, the liquid hydrocarbon produced in oil-refining chemical industry (reduced pressure distillation process as usual, catalytic cracking process, heavy oil catalytic cracking process or delay coking process) contains mercaptan, carbonylsulfide (COS), H
2S and CS
2Deng sulfocompound, these sulfocompounds can mix in the organic compound products such as propylene, propane or ethane that prepared by this liquid hydrocarbon, thereby have reduced the quality of the organic compound product of preparation.Therefore, in the described liquid hydrocarbon of employing is prepared with the process of organic compounds product, need to remove these sulfocompounds, to improve the purity of the organic compound product prepared.Yet, in actual production process, H
2Thereby S can generate the thioether that traditional organic sweetening agent is difficult to remove with olefine reaction, and COS and CS
2It itself is also the sulfocompound that adopts traditional organic sweetening agent to be difficult to remove.
For this reason, CN 101319149A discloses and a kind of liquid hydrocarbon that delayed coking unit produces has first been carried out to pre-treatment, then be re-used as the raw material of gas fractionation plant, process to produce the method for propylene, propane, C-4-fraction, wherein, utilize amine liquid to remove the coking liquid hydrocarbon of hydrogen sulfide before carrying out gas separation unit, first carry out the soda-wash water wash-out except mercaptan and remove a small amount of water, advance again the COS hydrolytic decomposition pot and carry out desulfurization, then remove again the hydrogen sulfide that hydrolysis produces, then air inlet body fractionation plant is processed as raw material.
In above-mentioned patent application, liquid hydrocarbon produces after the desulfurization of COS hydrolytic decomposition pot hydrogen sulfide is to adopt traditional hydrogen sulfide desulphurization agent to remove.Yet these traditional hydrogen sulfide desulphurization agents are difficult to fully remove the hydrogen sulfide in described liquid hydrocarbon, make the sulphur content in the organic compound product of final preparation still higher.
CN 1120970A discloses a kind of novel normal low-temp desulfurization agent, and it comprises that three kinds of following oxide weights form: ZnO 85-95%, Na
2O 0.1-10%, Al
2O
30.1-10%.Although the sweetening agent in this patent application has the ability that removes hydrogen sulfide of obvious raising with respect to amine liquid, yet, the Sulfur capacity of this sweetening agent is still not high, thereby, this sweetening agent still is difficult to prepare the organic compound products such as highly purified propylene for the process that liquid hydrocarbon prepares the organic compound products such as propylene.
Summary of the invention
The present invention adopts existing method to carry out to the thick product of propylene the defect that purifying is difficult to fully remove sulfocompound wherein in order to overcome, and a kind of purification process of the thick product of propylene that contains sulfocompound newly is provided.
The invention provides a kind of purification process that contains the thick product of propylene of sulfocompound, the method comprises contacts the thick product of propylene successively with sweetening agent with hydrolytic reagent, and described sweetening agent contains zinc oxide, sodium carbonate and tackiness agent.
According to method provided by the invention, by making the thick product of propylene, contact with hydrolytic reagent, the COS in the thick product of described propylene can be hydrolyzed into to H
2S, and by with described sweetening agent, contacting to remove H
2S and CS
2And the sweetening agent used in described method provided by the invention is owing to containing zinc oxide and sodium carbonate, thereby have very high Sulfur capacity, and then to H
2S and CS
2Has the very strong ability that removes.The propylene product that therefore, can prepare the higher degree that sulphur content is very low according to described method provided by the invention.In the present invention, described Sulfur capacity refers to the total amount of the sulphur of unit weight sweetening agent energy effective elimination.
Embodiment
According to the described purification process that contains the thick product of propylene of sulfocompound provided by the invention, comprise the thick product of propylene is contacted with sweetening agent with hydrolytic reagent successively, described sweetening agent contains zinc oxide, sodium carbonate and tackiness agent.
According to method provided by the invention, in the described thick product of propylene that contains sulfocompound, the content of described sulfocompound can in very large range change, and under preferable case, the content of described sulfocompound is below 100ppm.In this case, the content of the sulfocompound in the described thick product of propylene that contains sulfocompound can be reduced to below 2ppm according to method provided by the invention, thereby can obtain the propylene product of higher degree.In further preferred situation, the content of described sulfocompound is 10-100ppm.In the present invention, ppm refers to weight percent.
According to method provided by the invention, described sulfocompound can comprise hydrogen sulfide, carbonylsulfide and CS2 usually.
In described method provided by the invention, by making the thick product of described propylene, contact with described hydrolytic reagent, make the COS in the thick product of described propylene be hydrolyzed into carbonic acid gas and hydrogen sulfide, and described hydrogen sulfide can remove by follow-up sweetening agent.
In the present invention, there is no particular limitation for described hydrolytic reagent, as long as COS can be hydrolyzed into to hydrogen sulfide.Under preferable case, described hydrolytic reagent contains support of the catalyst and loads on the active ingredient on described support of the catalyst, and what described active ingredient can be in salt of wormwood, potassium hydroxide, sodium carbonate and sodium hydroxide is at least a.Further under preferable case, described active ingredient is salt of wormwood, and in this preferred implementation, described hydrolytic reagent has very high hydrolysis conversion to COS, thereby can significantly improve according to the removal effect of described method provided by the invention to COS.There is no particular limitation for the kind of described support of the catalyst, adopt the conventional various support of the catalyst of using in this area all can realize purpose of the present invention, what for example described support of the catalyst can be in aluminum oxide, silica gel and molecular sieve is at least a, and described molecular sieve for example can be the 13X molecular sieve.In the present invention, described hydrolysis conversion refers to the weight percent that COS is hydrolyzed and is converted into hydrogen sulfide.
In described hydrolytic reagent, with respect to the described support of the catalyst of 100 weight parts, the content of described active ingredient can be the 1-25 weight part, is preferably the 5-20 weight part.
In the present invention, there is no particular limitation for the condition that the thick product of described propylene contacts with described hydrolytic reagent, yet, in order to improve the hydrolysis conversion of COS in the thick product of described propylene, the thick product of described propylene comprises with the condition optimization that described hydrolytic reagent contacts: temperature is-10-80 ℃, more preferably 10-50 ℃; Pressure is 0.5-2.0MPa, more preferably 0.8-1.5MPa; The weight space velocity of the thick product of described propylene is 0.5-3h
-1, 0.8-2h more preferably
-1.In the situation that the thick product of described propylene contacts with described hydrolytic reagent, the weight space velocity of the thick product of described propylene refers to the weight of the thick product of propylene of the hydrolytic reagent that passes through unit weight in the unit time.
According to method provided by the invention, make to contact with described sweetening agent through the thick product of propylene with obtaining after described hydrolytic reagent contacts, thereby fully remove the H in the thick product of described propylene
2S and CS
2Deng sulfocompound.In the present invention, described sweetening agent contains zinc oxide, sodium carbonate and tackiness agent.In described sweetening agent, there is no particular limitation for the content of described zinc oxide, sodium carbonate and tackiness agent, yet, for making described sweetening agent have higher Sulfur capacity, thereby has the stronger ability that removes sulfocompound, the gross weight of described sweetening agent of take is benchmark, and the content of described zinc oxide is preferably the 65-90 % by weight, more preferably the 70-80 % by weight; The content of described sodium carbonate is preferably the 5-20 % by weight, more preferably the 10-15 % by weight; The content of described tackiness agent is preferably the 3-20 % by weight, more preferably the 5-15 % by weight.
In described sweetening agent, the tackiness agent in described sweetening agent can be the various tackiness agents that routine is used, for example can be in kaolin, sodium metaaluminate, the sweet soil of sheep and diatomite at least a.In the preferred case, described tackiness agent is sodium metaaluminate, thereby makes described sweetening agent have higher Sulfur capacity.
In the present invention, described sweetening agent can adopt conventional method preparation, for example can carry out moulding and activation by the raw mix that makes to contain zinc oxide, sodium carbonate and tackiness agent, thereby make.Yet, in order further to improve the Sulfur capacity of prepared sweetening agent, preferably in described raw mix, add zinc carbonate.Described zinc carbonate can play the reaming effect, thereby makes the sweetening agent of final preparation have pore volume and the bore dia of increase, and then improves the Sulfur capacity of described sweetening agent.
In the process of the described sweetening agent of preparation, the method for described activation can be included under inert gas atmosphere at 120-500 ℃ of lower thermal treatment 1-5 hour; In a kind of preferred implementation, in the situation that added zinc carbonate in the mixture of described zinc oxide, sodium carbonate and tackiness agent, the method for described activation is included under inert gas atmosphere at 350-450 ℃ of lower thermal treatment 1-5 hour.Described thermal treatment is to be positioned in the environment of said temperature scope (be 120-500 ℃, be preferably 350-450 ℃) and to implement by the forming composition obtained by after described moulding.Under above-mentioned activation condition, zinc carbonate decomposes, and generates carbonic acid gas and zinc oxide, and described zinc oxide is for the active ingredient of the described sweetening agent of supply.The gas of described rare gas element for not reacting with described zinc oxide, sodium carbonate and tackiness agent under 120-500 ℃.Described rare gas element can be in nitrogen, argon gas, helium and neon at least a.
In the process of the described sweetening agent of preparation, there is no particular limitation for the add-on of described zinc carbonate, yet, Sulfur capacity for the sweetening agent that significantly improves final preparation, mixture with respect to described zinc oxide, sodium carbonate and the tackiness agent of 100 weight parts, the add-on of described zinc carbonate is preferably the 1-15 weight part, more preferably the 3-12 weight part.
According to method provided by the invention, there is no particular limitation for the condition that the thick product of described propylene contacts with described sweetening agent, yet, in order fully to remove the sulfocompound in the thick product of described propylene, the thick product of described propylene comprises with the condition optimization that described sweetening agent contacts: temperature is 0-80 ℃, more preferably 10-50 ℃; Pressure is 0.5-2.0MPa, more preferably 0.8-1.5MPa; The weight space velocity of the thick product of described propylene is 0.5-3h
-1, 0.8-2h more preferably
-1.In the situation that the thick product of propylene contacts with described sweetening agent, the weight space velocity of the thick product of propylene refers to the weight of the thick product of propylene of the sweetening agent that passes through unit weight in the unit time.
In the present invention; the described thick product of propylene that contains sulfocompound can also contain water usually; water-content in the thick product of propylene is too high (for example, higher than 300ppm; more even higher than 500ppm) time; the thick product of this propylene is contacted with hydrolytic reagent, can greatly reduce the hydrolysis conversion of COS.Therefore, described method provided by the invention preferably also comprise make the thick product of propylene with dewater before described hydrolytic reagent contacts, to remove the part water in the thick product of described propylene, make reduced water content in the thick product of propylene to 10-300ppm, more preferably be reduced to 10-100ppm.In the present invention, there is no particular limitation for the method for described dehydration, can adopt conventional dewatering to implement.Under preferable case, the thick product of propylene is contacted with aluminum oxide and/or molecular sieve.There is no particular limitation in the present invention for described molecular sieve, for example can be 3A type molecular sieve and/or 4A type molecular sieve.
In further preferred embodiment, method according to the present invention also comprises makes the thick product of propylene with pre-sweetening agent, contact that the thick product of described propylene was carried out to pre-desulfurization before dehydration, this pre-sweetening process is mainly in order to remove in advance the hydrogen sulfide in the thick product of described propylene, to prevent that hydrogen sulfide from reacting with propylene, generate the thioether that is difficult to remove, and further improve the hydrolysis conversion of described hydrolytic reagent to COS.Described pre-sweetening agent can be the sweetening agent of the various routines that can remove hydrogen sulfide, yet, in the preferred case, described pre-sweetening agent is identical with aforesaid sweetening agent, be also that described pre-sweetening agent contains zinc oxide, sodium carbonate and tackiness agent, and the gross weight of described pre-sweetening agent of take is benchmark, and the content of described zinc oxide is preferably the 65-90 % by weight, more preferably the 70-80 % by weight; The content of described sodium carbonate is preferably the 5-20 % by weight, more preferably the 10-15 % by weight; The content of described tackiness agent is preferably the 3-20 % by weight, more preferably the 5-15 % by weight.Described tackiness agent is preferably at least a in kaolin, sodium metaaluminate, the sweet soil of sheep and diatomite.
In the present invention, the described thick product of propylene that contains sulfocompound can be for the propylene from obtaining liquid hydrocarbon thick product, what described liquid hydrocarbon can be in the liquid hydrocarbon produced in atmospheric and vacuum distillation technique, catalytic cracking process, heavy oil catalytic cracking process and delay coking process is at least a.There is no particular limitation from the method that obtains the thick product of propylene liquid hydrocarbon, for example can comprise liquid hydrocarbon is contacted with alkali lye with amine liquid for desulphurization successively, then wash, and the liquid hydrocarbon obtained after making to wash carries out fractionation, thereby obtain the thick product of propylene.
It is in order to remove the hydrogen sulfide in described liquid hydrocarbon that described liquid hydrocarbon is contacted with described amine liquid for desulphurization.There is no particular limitation for described amine liquid for desulphurization, the various amine liquid for desulphurization that can remove the hydrogen sulfide in liquid hydrocarbon all can be used in the present invention, what for example the amine in described amine liquid for desulphurization can be in thanomin, diethanolamine, diglycolamine and N methyldiethanol amine is at least a, the concentration of described amine liquid for desulphurization can be the 5-40 % by weight, is preferably the 10-30 % by weight.Further under preferable case, described amine liquid for desulphurization is the aqueous solution that contains the N methyldiethanol amine of 10-30 % by weight, more preferably contains the aqueous solution of the N methyldiethanol amine of 20-25 % by weight.The condition that described liquid hydrocarbon contacts with described amine liquid for desulphurization can comprise: temperature is 10-45 ℃, and pressure is 0.5-2MPa.In described liquid hydrocarbon and process that described amine liquid for desulphurization contacts, there is no particular limitation for the consumption of described amine liquid for desulphurization, can suitably adjust according to the content of the hydrogen sulfide in described liquid hydrocarbon, under preferable case, described liquid hydrocarbon with respect to 100 weight parts, the consumption of described amine liquid for desulphurization is the 5-60 weight part, more preferably the 20-45 weight part.
After making described liquid hydrocarbon and described amine liquid for desulphurization contacts to remove hydrogen sulfide, making to contact with described alkali lye through the liquid hydrocarbon that removes hydrogen sulfide is in order to remove mercaptan in described liquid hydrocarbon.Described alkali lye can be the aqueous solution of the sodium hydroxide that contains the 10-30 % by weight.The condition that described liquid hydrocarbon contacts with described alkali lye can comprise: temperature is-10-40 ℃ that pressure is 0.5-2MPa.In described liquid hydrocarbon and process that described alkali lye contacts, the consumption of described alkali lye can suitably be adjusted according to the content of the mercaptan in described liquid hydrocarbon, under preferable case, described liquid hydrocarbon with respect to 100 weight parts, the consumption of described amine liquid for desulphurization is the 10-30 weight part, more preferably the 20-25 weight part.
At described liquid hydrocarbon, be for mineral ion such as sodium ion in removing described liquid hydrocarbon with the water washing process after described alkali lye contacts.The condition of described washing can comprise: temperature is-10-40 ℃ ℃, and pressure is 0.5-2MPa, and with respect to the described liquid hydrocarbon of 100 weight parts, the consumption of described water is the 5-30 weight part.
The liquid hydrocarbon obtained after making to wash carries out the method for fractionation can be implemented in conventional gas fractionation plant, as long as its implementation condition can be by the propylene separation in described liquid hydrocarbon out.From the method for isolating propylene described liquid hydrocarbon, can adopt disclosed method in CN 1583971A to implement.
The invention will be further described by the following examples, but the present invention is not limited only to this.
Preparation example 1
Prepare sweetening agent
(a) sodium metaaluminate of the zinc carbonate of the sodium carbonate of the zinc oxide of 67 weight parts, 11 weight parts, 11 weight parts, 11 weight parts and appropriate water are mixed; make mixed slurry; then use the twin screw extruder extrusion moulding; and dry under 120 ℃; under 380 ℃, activating 2 hours under nitrogen protection afterwards; be cooled to afterwards room temperature, thereby obtain sweetening agent A1.
(b) kaolin of the zinc carbonate of the sodium carbonate of the zinc oxide of 65 weight parts, 14 weight parts, 7 weight parts, 14 weight parts and appropriate water are mixed; make mixed slurry; then use the twin screw extruder extrusion moulding; and dry under 120 ℃; under 450 ℃, activating 1.5 hours under nitrogen protection afterwards; be cooled to afterwards room temperature, thereby obtain sweetening agent A2.
(c) the sweet soil of sheep of the zinc carbonate of the sodium carbonate of the zinc oxide of 77 weight parts, 10 weight parts, 3 weight parts, 10 weight parts and appropriate water are mixed; make mixed slurry; then use the twin screw extruder extrusion moulding; and dry under 120 ℃; under 400 ℃, activating 2.5 hours under argon shield afterwards; be cooled to afterwards room temperature, thereby obtain sweetening agent A3.
(d) sodium metaaluminate of the zinc carbonate of the zinc oxide of 78 weight parts, 11 weight parts, 11 weight parts and appropriate water are mixed; make mixed slurry; then use the twin screw extruder extrusion moulding; and dry under 120 ℃; under 380 ℃, activating 2 hours under nitrogen protection afterwards; be cooled to afterwards room temperature, thereby obtain sweetening agent A4.
(e) by the zinc subcarbonate of 160 weight parts 400 ℃ of lower roastings 3 hours, add wherein the water of the sodium metaaluminate of sodium carboxymethylcellulose pyce, 9 weight parts of zinc subcarbonate, 1 weight part of 13 weight parts and 36 weight parts and mix, the mixture that then will obtain twin screw extruder extrusion moulding, dry under 100 ℃, then 400 ℃ of lower roastings 3 hours, thereby obtain containing the sweetening agent A5 of the aluminum oxide of the sodium oxide of zinc oxide, 2.81 % by weight of 92.57 % by weight and 4.62 % by weight.
Preparation example 2
Prepare hydrolytic reagent
(a) by the alumina supporter of 100 weight parts (purchased from Wuhan Hezhong Bio-chemical Manufature Co., Ltd., average pore diameter is 15 nanometers) thorough impregnation is in unsaturated carbonate potassium solution 2 hours, then make to adsorb the alumina supporter that solution of potassium carbonate is arranged dry under 100 ℃, with the salt of wormwood at described alumina supporter load 15 weight parts.Then, make load have the alumina supporter of salt of wormwood to activate 3 hours under the protection at nitrogen under 200 ℃, and be cooled to room temperature, thereby obtain hydrolytic reagent B1.
(b) by the 13X molecular sieve of 100 weight parts (purchased from Shanghai zeolite molecular sieve company limited) thorough impregnation in saturated sodium carbonate solution 1 hour, then making to adsorb has the 13X of sodium carbonate solution molecular sieve dry under 100 ℃, with the sodium carbonate of load 5 weight parts on the 13X molecular sieve.Then, make load have the 13X molecular sieve of sodium carbonate to activate 3 hours under the protection at nitrogen under 200 ℃, and be cooled to room temperature, thereby obtain hydrolytic reagent B2.
(c) by the alumina supporter of 100 weight parts (purchased from Wuhan Hezhong Bio-chemical Manufature Co., Ltd., average pore diameter is 15 nanometers) thorough impregnation is in potassium hydroxide solution 3 hours, then make to adsorb the alumina supporter that potassium hydroxide solution is arranged dry under 100 ℃, with the potassium hydroxide at described alumina supporter load 20 weight parts.Then, make load have the alumina supporter of potassium hydroxide to activate 2 hours under the protection at nitrogen under 200 ℃, and be cooled to room temperature, thereby obtain hydrolytic reagent B3.
Embodiment 1
The present embodiment is for illustrating the method for being obtained propylene by liquid hydrocarbon according to the present invention.
(1) prepare the crude propylene product
The aqueous solution that makes liquid hydrocarbon (forming as shown in table 1) and contain the N methyldiethanol amine of 23 % by weight enters in absorption tower, the inlet amount of described liquid hydrocarbon is 32 tons/hour, the inlet amount of the aqueous solution of described N methyldiethanol amine is 10 tons/hour, temperature in described absorption tower is 30 ℃, and pressure is 1.2MPa.Then, from the isolated liquid hydrocarbon in the bottom on described absorption tower and concentration be 20 % by weight the NaOH aqueous solution respectively from the bottom of tower and tower top enter extraction tower, the inlet amount of described liquid hydrocarbon is 35 tons/hour, the inlet amount of the described NaOH aqueous solution is 8 tons/hour, temperature in described extraction tower is 25 ℃, and pressure is 1.2MPa.Afterwards, isolated liquid hydrocarbon in described extraction tower is at room temperature washed, the consumption of water is 2 tons/hour.The liquid hydrocarbon obtained after making to wash enters in light ends tower and carries out fractionation, to obtain the thick product of propylene, records according to the method for GB3392-82 the sulfocompound that contains 28ppm in the thick product of described propylene.
(2) purifying of crude propylene
Make the thick product of propylene obtained in (1) take weight space velocity and be 1.0h
-1Enter successively in the preparation example 1 that is filled with 6 tons the sweetening agent A1 of preparation fixed-bed reactor a (aspect ratio is 4.5), be filled with 8 tons of aluminum oxide fixed-bed reactor b (aspect ratio is 4.5), be filled with the fixed-bed reactor c (aspect ratio is 4.5) of the hydrolytic reagent B 1 of preparation in 10 tons of preparation examples 2 and be filled with the fixed-bed reactor d (aspect ratio is 4.5) of the sweetening agent A1 prepared in the preparation example 1 of 10 tons of grams; Temperature in described fixed-bed reactor a is 5 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor b is 5 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor c is 5 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor d is 5 ℃, and pressure is 1.2MPa; The product of collection after described fixed-bed reactor d processes, as propylene product, records according to the method for GB3392-82 the sulfocompound that contains 1.0ppm in described propylene product.
Table 1
Embodiment 2
The present embodiment is for illustrating the method for being obtained propylene by liquid hydrocarbon according to the present invention.
(1) prepare the crude propylene product
The aqueous solution that makes liquid hydrocarbon (forming as shown in table 1) and contain the N methyldiethanol amine of 20 % by weight enters in absorption tower, the inlet amount of described liquid hydrocarbon is 30 tons/hour, the inlet amount of the aqueous solution of described N methyldiethanol amine is 15 tons/hour, temperature in described absorption tower is 40 ℃, and pressure is 1.2MPa.Then, from the isolated liquid hydrocarbon in the bottom on described absorption tower and concentration be 30 % by weight the NaOH aqueous solution respectively from the bottom of tower and tower top enter extraction tower, the inlet amount of described liquid hydrocarbon is 30 tons/hour, the inlet amount of the described NaOH aqueous solution is 4 tons/hour, temperature in described extraction tower is 25 ℃, and pressure is 1.2MPa.Afterwards, isolated liquid hydrocarbon in described extraction tower is at room temperature washed, the consumption of water is 2 tons/hour.The liquid hydrocarbon obtained after making to wash enters in light ends tower and carries out fractionation, to obtain the thick product of propylene, records according to the method for GB3392-82 the sulfocompound that contains 26ppm in the thick product of described propylene.
(2) purifying of crude propylene
Make the thick product of propylene obtained in (1) take weight space velocity and be 1.5h
-1Enter successively in the preparation example 1 that is filled with 8 tons the sweetening agent A2 of preparation fixed-bed reactor a (aspect ratio is 3.5), be filled with 12 tons of aluminum oxide fixed-bed reactor b (aspect ratio is 3.5), be filled with the fixed-bed reactor c (aspect ratio is 3.5) of the hydrolytic reagent B2 of preparation in 12 tons of preparation examples 2 and be filled with the fixed-bed reactor d (aspect ratio is 3.5) of the sweetening agent A2 prepared in the preparation example 1 of 12 tons; Temperature in described fixed-bed reactor a is 10 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor b is 10 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor c is 10 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor d is 10 ℃, and pressure is 1.2MPa; The product of collection after described fixed-bed reactor d processes, as propylene product, records according to the method for GB3392-82 the sulfocompound that contains 1.5ppm in described propylene product.
Embodiment 3
The present embodiment is for illustrating the method for being obtained propylene by liquid hydrocarbon according to the present invention.
(1) prepare the crude propylene product
The aqueous solution that makes liquid hydrocarbon (forming as shown in table 1) and contain the N methyldiethanol amine of 25 % by weight enters in absorption tower, the inlet amount of described liquid hydrocarbon is 35 tons/hour, the inlet amount of the aqueous solution of described N methyldiethanol amine is 8 tons/hour, temperature in described absorption tower is 25 ℃, and pressure is 1.2MPa.Then, from the isolated liquid hydrocarbon in the bottom on described absorption tower and concentration be 15 % by weight the NaOH aqueous solution respectively from the bottom of tower and tower top enter extraction tower, the inlet amount of described liquid hydrocarbon is 32 tons/hour, the inlet amount of the described NaOH aqueous solution is 12 tons/hour, temperature in described extraction tower is 25 ℃, and pressure is 1.2MPa.Afterwards, isolated liquid hydrocarbon in described extraction tower is at room temperature washed, the consumption of water is 2 tons/hour.The liquid hydrocarbon obtained after making to wash enters in light ends tower and carries out fractionation, to obtain the thick product of propylene, records according to the method for GB3392-82 the sulfocompound that contains 31ppm in the thick product of described propylene.
(2) purifying of crude propylene
Make the thick product of propylene obtained in (1) take weight space velocity and be 1.5h
-1Enter successively in the preparation example 1 that is filled with 8 tons the sweetening agent A3 of preparation fixed-bed reactor a (aspect ratio is 5), be filled with aluminum oxide fixed-bed reactor b (aspect ratio is 5), be filled with the fixed-bed reactor c (aspect ratio is 5) of the hydrolytic reagent B3 of preparation in 12 tons of preparation examples 2 and be filled with the fixed-bed reactor d (aspect ratio is 5) of the sweetening agent A3 prepared in the preparation example 1 of 12 tons; Temperature in described fixed-bed reactor a is 20 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor b is 20 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor c is 20 ℃, and pressure is 1.2MPa; Temperature in described fixed-bed reactor d is 20 ℃, and pressure is 1.2MPa; The product of collection after described fixed-bed reactor d processes be as propylene product, records in described propylene product and contain the propylene of 99.975 volume % and the sulfocompound of 1.6ppm according to the method for GB3392-82.
Embodiment 4
The present embodiment is for illustrating the method for being obtained propylene by liquid hydrocarbon according to the present invention.
According to the method for embodiment 1, prepare crude propylene and the purifying that carries out crude propylene, difference is, in the purge process of crude propylene, the thick product of propylene that makes to obtain in (1) enters described fixed-bed reactor c and described fixed-bed reactor d successively, and does not enter described fixed-bed reactor a and described fixed-bed reactor b.According to the method for GB3392-82, record from the propylene product of collecting described fixed-bed reactor d, containing the sulfocompound of 2.0ppm.
Comparative Examples 1
According to the method for embodiment 1, prepare crude propylene and the purifying that carries out crude propylene, difference is that in the purge process of crude propylene, the sweetening agent of loading in described fixed-bed reactor d is the sweetening agent A4 of preparation in preparation example 1.According to the method for GB3392-82, record from the propylene product of collecting described fixed-bed reactor d, containing the sulfocompound of 4.8ppm.
Comparative Examples 2
According to the method for embodiment 1, prepare crude propylene and the purifying that carries out crude propylene, difference is that in the purge process of crude propylene, the sweetening agent of loading in described fixed-bed reactor d is the sweetening agent A5 of preparation in preparation example 1.According to the method for GB3392-82, record from the propylene product of collecting described fixed-bed reactor d, containing the sulfocompound of 3.9ppm.
As can be seen here, according to the method for the thick purifying products of described propylene provided by the invention, can fully remove the sulfocompound in the thick product of propylene, thereby can prepare the propylene that purity is higher.
Claims (14)
1. purification process that contains the thick product of propylene of sulfocompound, it is characterized in that, the method comprises that the thick product of propylene that makes to contain sulfocompound contacts with sweetening agent with hydrolytic reagent successively, described sweetening agent contains zinc oxide, sodium carbonate and tackiness agent, wherein, in described sweetening agent, the content of described zinc oxide is the 65-90 % by weight, the content of described sodium carbonate is the 5-20 % by weight, and the content of described tackiness agent is the 3-20 % by weight.
2. method according to claim 1, wherein, in described sweetening agent, the content of described zinc oxide is the 70-80 % by weight, and the content of described sodium carbonate is the 10-15 % by weight, and the content of described tackiness agent is the 5-15 % by weight.
3. method according to claim 1 and 2, wherein, described tackiness agent is at least a in kaolin, sodium metaaluminate, the sweet soil of sheep and diatomite.
4. method according to claim 1, wherein, the thick product of described propylene comprises with the condition that described sweetening agent contacts: temperature is 0-80 ℃, and pressure is 0.5-2MPa, and the weight space velocity of the thick product of described propylene is 0.5-3h
-1.
5. according to the described method of claim 1 or 4, wherein, described hydrolytic reagent comprises support of the catalyst and loads on the active ingredient on described support of the catalyst, and described active ingredient is at least a in salt of wormwood, potassium hydroxide, sodium carbonate and sodium hydroxide.
6. method according to claim 5, wherein, in described hydrolytic reagent, with respect to the described support of the catalyst of 100 weight parts, the content of described active ingredient is the 1-25 weight part.
7. method according to claim 5, wherein, the thick product of described propylene comprises with the condition that described hydrolytic reagent contacts: temperature is-10-80 ℃, and pressure is 0.5-2.0MPa, and the weight space velocity of the thick product of described propylene is 0.5-3h
-1.
8. method according to claim 1, wherein, the method also comprise make the thick product of described propylene with dewater before described hydrolytic reagent contacts, make reduced water content in the thick product of propylene to 10-300ppm.
9. method according to claim 8, wherein, the method for described dehydration comprises makes the thick product of described propylene contact with aluminum oxide and/or molecular sieve.
10. according to claim 8 or claim 9 method, the method also comprise contacted the thick product of described propylene with sweetening agent in advance before dehydration.
11. method according to claim 10, wherein, described pre-sweetening agent contains zinc oxide, sodium carbonate and tackiness agent, and the gross weight of described pre-sweetening agent of take is benchmark, the content of described zinc oxide is the 65-90 % by weight, the content of described sodium carbonate is the 5-20 % by weight, and the content of described tackiness agent is the 3-20 % by weight.
12. method according to claim 11, wherein, the gross weight of described pre-sweetening agent of take is benchmark, and the content of described zinc oxide is the 70-80 % by weight, and the content of described sodium carbonate is the 10-15 % by weight, and the content of described tackiness agent is the 5-15 % by weight.
13. method according to claim 1, wherein, in the described thick product of propylene that contains sulfocompound, the content of described sulfocompound is 10-100ppm.
14. according to the described method of claim 1 or 13, wherein, described sulfocompound comprises hydrogen sulfide, carbonylsulfide and CS
2.
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| CN101255089A (en) * | 2008-04-03 | 2008-09-03 | 中国石油大学(北京) | Purification technique for producing propylene by refinery plant |
| CN101797477A (en) * | 2010-03-24 | 2010-08-11 | 太原理工大学 | Method for reducing concentration of carbonyl sulfide on outlet of hydrogen sulfide (H2S) desulfurizer |
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| CN101797477A (en) * | 2010-03-24 | 2010-08-11 | 太原理工大学 | Method for reducing concentration of carbonyl sulfide on outlet of hydrogen sulfide (H2S) desulfurizer |
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