CN102381924A - 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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- CN102381924A CN102381924A CN2010102740375A CN201010274037A CN102381924A CN 102381924 A CN102381924 A CN 102381924A CN 2010102740375 A CN2010102740375 A CN 2010102740375A CN 201010274037 A CN201010274037 A CN 201010274037A CN 102381924 A CN102381924 A CN 102381924A
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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 that produces in the 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 cpds products such as propylene, propane or ethane by this liquid hydrocarbon preparation, thereby have reduced the quality of the organic cpds product of preparation.Therefore,, need remove, to improve the organic cpds product gas purity of preparation to these sulfocompounds adopting said liquid hydrocarbon to prepare in the process of organic cpds product.Yet, in the 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 also is 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 been carried out pre-treatment earlier, then remakes the raw material into gas fractionation plant, processes the method for producing propylene, propane, C-4-fraction; Wherein, Utilize coking liquid hydrocarbon that amine liquid removes hydrogen sulfide before carrying out gas separation unit, carry out the alkali cleaning water elution earlier and remove mercaptan and remove less water, advance the COS hydrolytic decomposition pot again and carry out desulfurization; Then remove the hydrogen sulfide that hydrolysis produces again, air inlet body fractionation plant is processed as raw material again.
In above-mentioned patented claim, the hydrogen sulfide that produces after the desulfurization of liquid hydrocarbon process COS hydrolytic decomposition pot 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 the said liquid hydrocarbon, make that the sulphur content in the final organic cpds product for preparing is still higher.
CN 1120970A discloses a kind of novel normal low-temp desulfurization agent, and it comprises three kinds of following oxide weights compositions: ZnO 85-95%, Na
2O 0.1-10%, Al
2O
30.1-10%.Though the sweetening agent in this patented claim 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 is used for the process that liquid hydrocarbon prepares organic cpds products such as propylene still is difficult to prepare organic cpds products such as highly purified propylene.
Summary of the invention
The present invention adopts existing method that the thick product of propylene is carried out the defective 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, this method comprises contacts the thick product of propylene successively with sweetening agent with hydrolytic reagent, and said sweetening agent contains zinc oxide, yellow soda ash and tackiness agent.
According to method provided by the invention, contact with hydrolytic reagent through making the thick product of propylene, can the COS in the thick product of said propylene be hydrolyzed into H
2S, and through contacting to remove H with said sweetening agent
2S and CS
2And the sweetening agent that uses in the said method provided by the invention is owing to contain zinc oxide and yellow soda ash, thereby has 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 very low higher degree of sulphur content according to said method provided by the invention.In the present invention, said Sulfur capacity is meant the total amount of the sulphur of unit weight sweetening agent ability effective elimination.
Embodiment
Comprise according to the said purification process that contains the thick product of propylene of sulfocompound provided by the invention the thick product of propylene is contacted with sweetening agent with hydrolytic reagent successively, said sweetening agent contains zinc oxide, yellow soda ash and tackiness agent.
According to method provided by the invention, in the said thick product of propylene that contains sulfocompound, the content of said sulfocompound can in very large range change, and under the preferable case, the content of said sulfocompound is below the 100ppm.In this case, can the content of the sulfocompound in the said thick product of propylene that contains sulfocompound be reduced to below the 2ppm, thereby can obtain the propylene product of higher degree according to method provided by the invention.Under further preferred situation, the content of said sulfocompound is 10-100ppm.In the present invention, ppm is meant weight percent.
According to method provided by the invention, said sulfocompound can comprise hydrogen sulfide, carbonylsulfide and CS2 usually.
In said method provided by the invention, contact with said hydrolytic reagent through making the thick product of said propylene, make that the COS in the thick product of said propylene is hydrolyzed into carbonic acid gas and hydrogen sulfide, and said hydrogen sulfide can remove through follow-up sweetening agent.
In the present invention, said hydrolytic reagent does not have special qualification, as long as can COS be hydrolyzed into hydrogen sulfide.Under the preferable case, said hydrolytic reagent contains support of the catalyst and loads on the active ingredient on the said support of the catalyst, and what said active ingredient can be in salt of wormwood, Pottasium Hydroxide, yellow soda ash and the sodium hydroxide is at least a.Further under the preferable case, said active ingredient is a salt of wormwood, and in this preferred implementation, said hydrolytic reagent has very high hydrolysis conversion to COS, thereby can significantly improve according to the removal effect of said method provided by the invention to COS.The kind of said support of the catalyst does not have special qualification; Adopt the conventional various support of the catalyst of using in this area all can realize the object of the invention; For example said support of the catalyst can be in aluminum oxide, silica gel and the molecular sieve at least a, said molecular sieve for example can be the 13X molecular sieve.In the present invention, said hydrolysis conversion is meant the COS hydrolysis and is converted into the weight percent of hydrogen sulfide.
In said hydrolytic reagent, with respect to the said support of the catalyst of 100 weight parts, the content of said active ingredient can be the 1-25 weight part, is preferably the 5-20 weight part.
In the present invention; The condition that the thick product of said propylene contacts with said hydrolytic reagent does not have special qualification; Yet; In order to improve the hydrolysis conversion of COS in the thick product of said propylene, the thick product of said propylene comprises with the condition optimization that said hydrolytic reagent contacts: temperature further is preferably 10-50 ℃ for-10-80 ℃; Pressure is 0.5-2.0MPa, further is preferably 0.8-1.5MPa; The weight space velocity of the thick product of said propylene is 0.5-3h
-1, further be preferably 0.8-2h
-1Under the thick product of said propylene and situation that said hydrolytic reagent contacts, the weight space velocity of the thick product of said propylene is meant in the unit time weight through the thick product of propylene of the hydrolytic reagent of unit weight.
According to method provided by the invention, the thick product of propylene that obtains after making process and said hydrolytic reagent contacting contacts with said sweetening agent, thereby fully removes the H in the thick product of said propylene
2S and CS
2Deng sulfocompound.In the present invention, said sweetening agent contains zinc oxide, yellow soda ash and tackiness agent.In said sweetening agent; The content of said zinc oxide, yellow soda ash and tackiness agent does not have special qualification, yet, have higher Sulfur capacity for making said sweetening agent; Thereby has the stronger ability that removes sulfocompound; Gross weight with said sweetening agent is a benchmark, and the content of said zinc oxide is preferably 65-90 weight %, further is preferably 70-80 weight %; The content of said yellow soda ash is preferably 5-20 weight %, further is preferably 10-15 weight %; The content of said tackiness agent is preferably 3-20 weight %, further is preferably 5-15 weight %.
In said sweetening agent, the tackiness agent in the said 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 the zeyssatite at least a.Under preferable case, said tackiness agent is a sodium metaaluminate, thereby makes said sweetening agent have higher Sulfur capacity.
In the present invention, said sweetening agent can adopt conventional method preparation, for example can carry out moulding and activation through making the raw mix that contains zinc oxide, yellow soda ash and tackiness agent, thereby make.Yet,, preferably in said raw mix, add zinc carbonate in order further to improve the Sulfur capacity of prepared sweetening agent.Said zinc carbonate can play the reaming effect, thereby makes the sweetening agent of final preparation have the pore volume and the bore dia of increase, and then improves the Sulfur capacity of said sweetening agent.
In the process of the said sweetening agent of preparation, said activatory method can be included under the inert gas atmosphere at 120-500 ℃ of following thermal treatment 1-5 hour; In a kind of preferred implementation, in the mixture of said zinc oxide, yellow soda ash and tackiness agent, added under the situation of zinc carbonate, said activatory method was included under the inert gas atmosphere at 350-450 ℃ of following thermal treatment 1-5 hour.Said thermal treatment is through implementing in the environment that the forming composition that obtains after the said moulding is positioned over said temperature scope (be 120-500 ℃, be preferably 350-450 ℃).Under above-mentioned activation condition, zinc carbonate decomposes, and generates carbonic acid gas and zinc oxide, and said zinc oxide is used for the active ingredient of the said sweetening agent of supply.The gas of said rare gas element under 120-500 ℃, not reacting with said zinc oxide, yellow soda ash and tackiness agent.Said rare gas element can be in nitrogen, argon gas, helium and the neon at least a.
In the process of the said sweetening agent of preparation; The add-on of said zinc carbonate does not have special qualification; Yet, for the Sulfur capacity of the sweetening agent that significantly improves final preparation, with respect to the mixture of said zinc oxide, yellow soda ash and the tackiness agent of 100 weight parts; The add-on of said zinc carbonate is preferably the 1-15 weight part, more preferably the 3-12 weight part.
According to method provided by the invention; The condition that the thick product of said propylene contacts with said sweetening agent does not have special qualification; Yet; In order fully to remove the sulfocompound in the thick product of said propylene, the thick product of said propylene comprises with the condition optimization that said sweetening agent contacts: temperature is 0-80 ℃, further is preferably 10-50 ℃; Pressure is 0.5-2.0MPa, further is preferably 0.8-1.5MPa; The weight space velocity of the thick product of said propylene is 0.5-3h
-1, further be preferably 0.8-2h
-1Under the thick product of propylene and situation that said sweetening agent contacts, the weight space velocity of the thick product of propylene is meant in the unit time weight through the thick product of propylene of the sweetening agent of unit weight.
In the present invention; The said 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 to be higher than 300ppm; More in addition be higher than 500ppm) time, the thick product of this propylene is contacted with hydrolytic reagent, then can reduce the hydrolysis conversion of COS greatly.Therefore; Said method provided by the invention preferably also comprises dewatered the thick product of propylene before contacting with said hydrolytic reagent; To remove the portion water in the thick product of said propylene, make that the water-content in the thick product of propylene is reduced to 10-300ppm, more preferably be reduced to 10-100ppm.In the present invention, said dehydration method does not have special qualification, can adopt conventional dewatering to implement.Under the preferable case, the thick product of propylene is contacted with aluminum oxide and/or molecular sieve.Said molecular sieve does not have special qualification in the present invention, 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 contacted so that the thick product of said propylene is carried out preparatory desulfurization the thick product of propylene with preparatory sweetening agent before dehydration; This preparatory sweetening process mainly is in order to remove the hydrogen sulfide in the thick product of said propylene in advance; With the thioether that prevents that hydrogen sulfide and propylene reaction generation is difficult to remove, and further improve the hydrolysis conversion of said hydrolytic reagent to COS.Said preparatory sweetening agent can be the sweetening agent of the various routines that can remove hydrogen sulfide; Yet under preferable case, said preparatory sweetening agent is identical with aforesaid sweetening agent; Also be that said preparatory sweetening agent contains zinc oxide, yellow soda ash and tackiness agent; And the gross weight with said preparatory sweetening agent is a benchmark, and the content of said zinc oxide is preferably 65-90 weight %, further is preferably 70-80 weight %; The content of said yellow soda ash is preferably 5-20 weight %, further is preferably 10-15 weight %; The content of said tackiness agent is preferably 3-20 weight %, further is preferably 5-15 weight %.Said tackiness agent is preferably at least a in kaolin, sodium metaaluminate, the sweet soil of sheep and the zeyssatite.
In the present invention; The said thick product of propylene that contains sulfocompound can be for the propylene that from liquid hydrocarbon, obtains thick product, what said liquid hydrocarbon can be in the liquid hydrocarbon that produces in atmospheric and vacuum distillation technology, catalytic cracking process, heavy oil catalytic cracking process and the delay coking process is at least a.The method that from liquid hydrocarbon, obtains the thick product of propylene does not have special qualification, for example can comprise liquid hydrocarbon is contacted with alkali lye with amine liquid for desulphurization successively, washes then, and makes the liquid hydrocarbon that obtains after the washing carry out fractionation, thereby obtain the thick product of propylene.
It is in order to remove the hydrogen sulfide in the said liquid hydrocarbon that said liquid hydrocarbon is contacted with said amine liquid for desulphurization.Said amine liquid for desulphurization does not have special qualification; The various amine liquid for desulphurization that can remove the hydrogen sulfide in the liquid hydrocarbon all can be used among the present invention; Amine in the for example said amine liquid for desulphurization can be in thanomin, diethylolamine, diglycolamine and the N methyldiethanol amine at least a; The concentration of said amine liquid for desulphurization can be 5-40 weight %, is preferably 10-30 weight %.Further under the preferable case, said amine liquid for desulphurization is the aqueous solution that contains the N methyldiethanol amine of 10-30 weight %, more preferably contains the aqueous solution of the N methyldiethanol amine of 20-25 weight %.The condition that said liquid hydrocarbon contacts with said amine liquid for desulphurization can comprise: temperature is 10-45 ℃, and pressure is 0.5-2MPa.In said liquid hydrocarbon and process that said amine liquid for desulphurization contacts; The consumption of said amine liquid for desulphurization does not have special qualification; Can suitably adjust according to the content of the hydrogen sulfide in the said liquid hydrocarbon, under the preferable case, with respect to the said liquid hydrocarbon of 100 weight parts; The consumption of said amine liquid for desulphurization is the 5-60 weight part, further is preferably the 20-45 weight part.
Said liquid hydrocarbon is contacted with after removing hydrogen sulfide with said amine liquid for desulphurization, and it is in order to remove mercaptan in the said liquid hydrocarbon that the liquid hydrocarbon that makes process remove hydrogen sulfide contacts with said alkali lye.Said alkali lye can be the aqueous solution of the sodium hydroxide that contains 10-30 weight %.The condition that said liquid hydrocarbon contacts with said alkali lye can comprise: temperature is-10-40 ℃, and pressure is 0.5-2MPa.In said liquid hydrocarbon and process that said alkali lye contacts; The consumption of said alkali lye can suitably be adjusted according to the content of the mercaptan in the said liquid hydrocarbon; Under the preferable case; With respect to the said liquid hydrocarbon of 100 weight parts, the consumption of said amine liquid for desulphurization is the 10-30 weight part, further is preferably the 20-25 weight part.
Is in order to remove mineral ion such as the sodium ion in the said liquid hydrocarbon at said liquid hydrocarbon with water washing process after said alkali lye contacts.The condition of said washing can comprise: temperature is-10-40 ℃ ℃, and pressure is 0.5-2MPa, and with respect to the said liquid hydrocarbon of 100 weight parts, the consumption of said water is the 5-30 weight part.
Making the liquid hydrocarbon that obtains after the washing carry out fractionated method can implement in the gas fractionation plant of routine, as long as its implementation condition can be separated the propylene in the said liquid hydrocarbon.The method of from said liquid hydrocarbon, isolating propylene can adopt disclosed method enforcement among the CN 1583971A.
Below through embodiment the present invention is described further, but the present invention is not limited only to this.
Preparation example 1
The preparation sweetening agent
(a) zinc oxide, 11 weight parts of sodium carbonate, the zinc carbonate of 11 weight parts, the sodium metaaluminate of 11 weight parts and an amount of water with 67 weight parts mixes; Process mixed slurry; Use the twin screw extruder extrusion moulding then, and 120 ℃ down dry, afterwards in activation 2 hours under nitrogen protection under 380 ℃; Be cooled to room temperature afterwards, thereby obtain sweetening agent A1.
(b) zinc oxide, 14 weight parts of sodium carbonate, the zinc carbonate of 7 weight parts, the kaolin of 14 weight parts and an amount of water with 65 weight parts mixes; Process mixed slurry; Use the twin screw extruder extrusion moulding then, and 120 ℃ down dry, afterwards in activation 1.5 hours under nitrogen protection under 450 ℃; Be cooled to room temperature afterwards, thereby obtain sweetening agent A2.
(c) zinc oxide, 10 weight parts of sodium carbonate, the zinc carbonate of 3 weight parts, the sweet soil of sheep of 10 weight parts and an amount of water with 77 weight parts mixes; Process mixed slurry; Use the twin screw extruder extrusion moulding then, and 120 ℃ down dry, afterwards in activation 2.5 hours under argon shield under 400 ℃; Be cooled to room temperature afterwards, thereby obtain sweetening agent A3.
(d) zinc oxide of 78 weight parts, the zinc carbonate of 11 weight parts, the sodium metaaluminate of 11 weight parts and an amount of water are mixed; Process mixed slurry; Use the twin screw extruder extrusion moulding then, and 120 ℃ down dry, afterwards in activation 2 hours under nitrogen protection under 380 ℃; Be cooled to room temperature afterwards, thereby obtain sweetening agent A4.
(e) with the zinc subcarbonate of 160 weight parts 400 ℃ of following roastings 3 hours; To the water of the sodium metaaluminate of the sodium carboxymethylcellulose pyce of the zinc subcarbonate that wherein adds 13 weight parts, 1 weight part, 9 weight parts and 36 weight parts and mix; Then the mixture that obtains is used the twin screw extruder extrusion moulding; Dry down at 100 ℃; Then 400 ℃ of following roastings 3 hours, thereby obtain containing the sweetening agent A5 of aluminum oxide of sodium oxide and 4.62 weight % of zinc oxide, the 2.81 weight % of 92.57 weight %.
Preparation example 2
The preparation hydrolytic reagent
(a) with the alumina supporter of 100 weight parts (available from Wuhan Hezhong Bio-chemical Manufature Co., Ltd.; Average pore diameter is 15 nanometers) thorough impregnation is in unsaturated carbonate potassium solution 2 hours; Make the alumina supporter that is adsorbed with solution of potassium carbonate dry under 100 ℃ then, with salt of wormwood at said alumina supporter load 15 weight parts.Then, make alumina supporter that load has salt of wormwood in activation 3 hours under protection of nitrogen gas under 200 ℃, and be cooled to room temperature, thereby obtain hydrolytic reagent B1.
(b) with 13X molecular sieve (available from the Shanghai zeolite molecular sieve ltd) thorough impregnation of 100 weight parts in saturated sodium carbonate solution 1 hour; Make the 13X molecular sieve that is adsorbed with sodium carbonate solution dry under 100 ℃ then, with load 5 weight parts of sodium carbonate on the 13X molecular sieve.Then, make 13X molecular sieve that load has yellow soda ash in activation 3 hours under protection of nitrogen gas under 200 ℃, and be cooled to room temperature, thereby obtain hydrolytic reagent B2.
(c) with the alumina supporter of 100 weight parts (available from Wuhan Hezhong Bio-chemical Manufature Co., Ltd.; Average pore diameter is 15 nanometers) thorough impregnation is in potassium hydroxide solution 3 hours; Make the alumina supporter that is adsorbed with potassium hydroxide solution dry under 100 ℃ then, with Pottasium Hydroxide at said alumina supporter load 20 weight parts.Then, make alumina supporter that load has Pottasium Hydroxide in activation 2 hours under protection of nitrogen gas under 200 ℃, and be cooled to room temperature, thereby obtain hydrolytic reagent B3.
Embodiment 1
Present embodiment is used to explain the method for being obtained propylene by liquid hydrocarbon according to the present invention.
(1) preparation crude propylene product
The aqueous solution that makes liquid hydrocarbon (forming as shown in table 1) and contain the N methyldiethanol amine of 23 weight % gets in the absorption tower; The inlet amount of said liquid hydrocarbon is 32 tons/hour; The inlet amount of the aqueous solution of said N methyldiethanol amine is 10 tons/hour; Temperature in the said absorption tower is 30 ℃, and pressure is 1.2MPa.Then; From the isolated liquid hydrocarbon in the bottom on said absorption tower and concentration is that the NaOH aqueous solution of 20 weight % gets into the extraction tower with cat head at the bottom of tower respectively; The inlet amount of said liquid hydrocarbon is 35 tons/hour; The inlet amount of the said NaOH aqueous solution is 8 tons/hour, and the temperature in the said extraction tower is 25 ℃, and pressure is 1.2MPa.Afterwards, isolated liquid hydrocarbon is at room temperature washed, the consumption of water is 2 tons/hour.The liquid hydrocarbon that obtains after the washing is got in the light ends tower carry out fractionation, obtaining the thick product of propylene, record the sulfocompound that contains 28ppm in the thick product of said propylene according to the method for GB3392-82.
(2) purifying of crude propylene
Making the thick product of propylene that obtains in (1) is 1.0h with the weight space velocity
-1Get into the fixed-bed reactor d (aspect ratio is 4.5) of the sweetening agent A1 for preparing in the fixed-bed reactor a (aspect ratio is 4.5) of the sweetening agent A1 of preparation in the preparation example 1 be filled with 6 tons, the fixed-bed reactor b (aspect ratio is 4.5) that is filled with 8 tons of aluminum oxide, fixed-bed reactor c (aspect ratio is 4.5) that is filled with the hydrolytic reagent B 1 of preparation in 10 tons of preparation examples 2 and the preparation example 1 that is filled with 10 tons of grams successively; Temperature in the said fixed-bed reactor a is 5 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor b is 5 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor c is 5 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor d is 5 ℃, and pressure is 1.2MPa; Collect product after handling through said fixed-bed reactor d as propylene product, record the sulfocompound that contains 1.0ppm in the said propylene product according to the method for GB3392-82.
Table 1
Embodiment 2
Present embodiment is used to explain the method for being obtained propylene by liquid hydrocarbon according to the present invention.
(1) preparation crude propylene product
The aqueous solution that makes liquid hydrocarbon (forming as shown in table 1) and contain the N methyldiethanol amine of 20 weight % gets in the absorption tower; The inlet amount of said liquid hydrocarbon is 30 tons/hour; The inlet amount of the aqueous solution of said N methyldiethanol amine is 15 tons/hour; Temperature in the said absorption tower is 40 ℃, and pressure is 1.2MPa.Then; From the isolated liquid hydrocarbon in the bottom on said absorption tower and concentration is that the NaOH aqueous solution of 30 weight % gets into the extraction tower with cat head at the bottom of tower respectively; The inlet amount of said liquid hydrocarbon is 30 tons/hour; The inlet amount of the said NaOH aqueous solution is 4 tons/hour, and the temperature in the said extraction tower is 25 ℃, and pressure is 1.2MPa.Afterwards, isolated liquid hydrocarbon is at room temperature washed, the consumption of water is 2 tons/hour.The liquid hydrocarbon that obtains after the washing is got in the light ends tower carry out fractionation, obtaining the thick product of propylene, record the sulfocompound that contains 26ppm in the thick product of said propylene according to the method for GB3392-82.
(2) purifying of crude propylene
Making the thick product of propylene that obtains in (1) is 1.5h with the weight space velocity
-1Get into the fixed-bed reactor a (aspect ratio is 3.5) of the sweetening agent A2 of preparation in the preparation example 1 be filled with 8 tons, the fixed-bed reactor b (aspect ratio is 3.5) that is filled with 12 tons of aluminum oxide, fixed-bed reactor c (aspect ratio is 3.5) that is filled with the hydrolytic reagent B2 of preparation in 12 tons of preparation examples 2 and the fixed-bed reactor d (aspect ratio is 3.5) that is filled with the sweetening agent A2 for preparing in 12 tons the preparation example 1 successively; Temperature in the said fixed-bed reactor a is 10 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor b is 10 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor c is 10 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor d is 10 ℃, and pressure is 1.2MPa; Collect product after handling through said fixed-bed reactor d as propylene product, record the sulfocompound that contains 1.5ppm in the said propylene product according to the method for GB3392-82.
Embodiment 3
Present embodiment is used to explain the method for being obtained propylene by liquid hydrocarbon according to the present invention.
(1) preparation crude propylene product
The aqueous solution that makes liquid hydrocarbon (forming as shown in table 1) and contain the N methyldiethanol amine of 25 weight % gets in the absorption tower; The inlet amount of said liquid hydrocarbon is 35 tons/hour; The inlet amount of the aqueous solution of said N methyldiethanol amine is 8 tons/hour; Temperature in the said absorption tower is 25 ℃, and pressure is 1.2MPa.Then; From the isolated liquid hydrocarbon in the bottom on said absorption tower and concentration is that the NaOH aqueous solution of 15 weight % gets into the extraction tower with cat head at the bottom of tower respectively; The inlet amount of said liquid hydrocarbon is 32 tons/hour; The inlet amount of the said NaOH aqueous solution is 12 tons/hour, and the temperature in the said extraction tower is 25 ℃, and pressure is 1.2MPa.Afterwards, isolated liquid hydrocarbon is at room temperature washed, the consumption of water is 2 tons/hour.The liquid hydrocarbon that obtains after the washing is got in the light ends tower carry out fractionation, obtaining the thick product of propylene, record the sulfocompound that contains 31ppm in the thick product of said propylene according to the method for GB3392-82.
(2) purifying of crude propylene
Making the thick product of propylene that obtains in (1) is 1.5h with the weight space velocity
-1Get into the fixed-bed reactor a (aspect ratio is 5) of the sweetening agent A3 of preparation in the preparation example 1 be filled with 8 tons, the fixed-bed reactor b (aspect ratio is 5) that is filled with aluminum oxide, fixed-bed reactor c (aspect ratio is 5) that is filled with the hydrolytic reagent B3 of preparation in 12 tons of preparation examples 2 and the fixed-bed reactor d (aspect ratio is 5) that is filled with the sweetening agent A3 for preparing in 12 tons the preparation example 1 successively; Temperature in the said fixed-bed reactor a is 20 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor b is 20 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor c is 20 ℃, and pressure is 1.2MPa; Temperature in the said fixed-bed reactor d is 20 ℃, and pressure is 1.2MPa; Collect product after handling through said fixed-bed reactor d as propylene product, record according to the method for GB3392-82 and contain the propylene of 99.975 volume % and the sulfocompound of 1.6ppm in the said propylene product.
Embodiment 4
Present embodiment is used to explain the method for being obtained propylene by liquid hydrocarbon according to the present invention.
Method according to embodiment 1 prepares crude propylene and the purifying that carries out crude propylene; Different is; In the purge process of crude propylene; Make the thick product of propylene that obtains in (1) get into said fixed-bed reactor c and said fixed-bed reactor d successively, and do not get into said fixed-bed reactor a and said fixed-bed reactor b.Method according to GB3392-82 records the sulfocompound that contains 2.0ppm in the propylene product of from said fixed-bed reactor d, collecting.
Comparative Examples 1
Method according to embodiment 1 prepares crude propylene and the purifying that carries out crude propylene, and different is that in the purge process of crude propylene, the sweetening agent of loading among the said fixed-bed reactor d is the sweetening agent A4 of preparation in the preparation example 1.Method according to GB3392-82 records the sulfocompound that contains 4.8ppm in the propylene product of from said fixed-bed reactor d, collecting.
Comparative Examples 2
Method according to embodiment 1 prepares crude propylene and the purifying that carries out crude propylene, and different is that in the purge process of crude propylene, the sweetening agent of loading among the said fixed-bed reactor d is the sweetening agent A5 of preparation in the preparation example 1.Method according to GB3392-82 records the sulfocompound that contains 3.9ppm in the propylene product of from said fixed-bed reactor d, collecting.
This shows, can fully remove the sulfocompound in the thick product of propylene according to the method for the thick purifying products of said propylene provided by the invention, thereby can prepare the higher propylene of purity.
Claims (15)
1. a purification process that contains the thick product of propylene of sulfocompound is characterized in that, this method comprises contacts the thick product of the propylene that contains sulfocompound successively with sweetening agent with hydrolytic reagent, and said sweetening agent contains zinc oxide, yellow soda ash and tackiness agent.
2. method according to claim 1, wherein, in said sweetening agent, the content of said zinc oxide is 65-90 weight %, and the content of said yellow soda ash is 5-20 weight %, and the content of said tackiness agent is 3-20 weight %.
3. method according to claim 2, wherein, in said sweetening agent, the content of said zinc oxide is 70-80 weight %, and the content of said yellow soda ash is 10-15 weight %, and the content of said tackiness agent is 5-15 weight %.
4. according to any described method among the claim 1-3, wherein, said tackiness agent is at least a in kaolin, sodium metaaluminate, the sweet soil of sheep and the zeyssatite.
5. method according to claim 1, wherein, the thick product of said propylene comprises with the condition that said sweetening agent contacts: temperature is 0-80 ℃, and pressure is 0.5-2MPa, and the weight space velocity of the thick product of said propylene is 0.5-3h
-1
6. according to claim 1 or 5 described methods, wherein, said hydrolytic reagent comprises support of the catalyst and loads on the active ingredient on the said support of the catalyst, and said active ingredient is at least a in salt of wormwood, Pottasium Hydroxide, yellow soda ash and the sodium hydroxide.
7. method according to claim 6, wherein, in said hydrolytic reagent, with respect to the said support of the catalyst of 100 weight parts, the content of said active ingredient is the 1-25 weight part.
8. method according to claim 6, wherein, the thick product of said propylene comprises with the condition that said hydrolytic reagent contacts: temperature is-10-80 ℃, and pressure is 0.5-2.0MPa, and the weight space velocity of the thick product of said propylene is 0.5-3h
-1
9. method according to claim 1, wherein, this method also comprises dewatered the thick product of said propylene before contacting with said hydrolytic reagent, make that the water-content in the thick product of propylene is reduced to 10-300ppm.
10. method according to claim 9, wherein, said dehydration method comprises makes the thick product of said propylene contact with aluminum oxide and/or molecular sieve.
11. according to claim 9 or 10 described methods, this method also comprises contacted the thick product of said propylene with preparatory sweetening agent before dehydration.
12. method according to claim 11; Wherein, Said preparatory sweetening agent contains zinc oxide, yellow soda ash and tackiness agent, and is benchmark with the gross weight of said preparatory sweetening agent, and the content of said zinc oxide is 65-90 weight %; The content of said yellow soda ash is 5-20 weight %, and the content of said tackiness agent is 3-20 weight %.
13. method according to claim 12 wherein, is a benchmark with the gross weight of said preparatory sweetening agent, the content of said zinc oxide is 70-80 weight %, and the content of said yellow soda ash is 10-15 weight %, and the content of said tackiness agent is 5-15 weight %.
14. method according to claim 1, wherein, in the said thick product of propylene that contains sulfocompound, the content of said sulfocompound is 10-100ppm.
15. according to claim 1 or 14 described methods, wherein, said sulfocompound comprises hydrogen sulfide, carbonylsulfide and CS
2
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0401789A1 (en) * | 1989-06-07 | 1990-12-12 | Phillips Petroleum Company | Selective removal of hydrogen sulfide over a zinc oxide and diatomite absorbing composition |
| CN101255089A (en) * | 2008-04-03 | 2008-09-03 | 中国石油大学(北京) | Purification technique for producing propylene by refinery plant |
| CN101590360A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of modified high temperature desulfuration agent and preparation method thereof |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0401789A1 (en) * | 1989-06-07 | 1990-12-12 | Phillips Petroleum Company | Selective removal of hydrogen sulfide over a zinc oxide and diatomite absorbing composition |
| CN101255089A (en) * | 2008-04-03 | 2008-09-03 | 中国石油大学(北京) | Purification technique for producing propylene by refinery plant |
| CN101590360A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of modified high temperature desulfuration agent and preparation method thereof |
| 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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