CN110407660B - Pretreatment process and pretreatment system for raw material C4 for solid acid alkylation process - Google Patents
Pretreatment process and pretreatment system for raw material C4 for solid acid alkylation process Download PDFInfo
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- 239000002994 raw material Substances 0.000 title claims abstract description 188
- 238000000034 method Methods 0.000 title claims abstract description 88
- 230000008569 process Effects 0.000 title claims abstract description 79
- 238000005804 alkylation reaction Methods 0.000 title abstract description 52
- 239000011973 solid acid Substances 0.000 title abstract description 43
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- 150000001336 alkenes Chemical class 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a pretreatment process of a raw material C4, which comprises the following steps of firstly, washing and dehydrating the raw material C4 to obtain a one-step treatment product; then, adsorbing the one-step treatment product obtained in the step to obtain a second-step treatment product without toxin; carrying out hydrogenation operation on the two-step treated product obtained in the step, removing light hydrocarbon and oxygen-containing compounds, and carrying out comprehensive adsorption treatment to obtain a three-step treated product; and finally, dehydrating the product obtained in the three steps again to obtain the pretreated raw material C4. The comprehensive pretreatment process for the post-C4 of the raw material ether for alkylation of the solid acid can effectively reduce and remove harmful impurities, completely meet the requirements of the solid acid catalyst on raw material components, greatly improve the stability of continuous production and obviously reduce the production cost. And the process is simple and easy to control, the conditions are mild, and the method is suitable for industrial popularization and application.
Description
Technical Field
The invention relates to the technical field of solid acid alkylation processes, relates to a pretreatment process and a pretreatment system for raw material C4, and particularly relates to a pretreatment process and a pretreatment system for raw material C4 for a solid acid alkylation process.
Background
The alkylate oil is a hydrocarbon-containing product in the petroleum refining process, is a very ideal and most clean high-octane gasoline blending component, is synthesized by alkylating isoparaffin and olefin (mainly isobutane and butylene) generated in petroleum processing (such as a thermal cracking or catalytic cracking process) under the action of a strong acid catalyst (sulfuric acid or hydrofluoric acid), has a motor octane number of over 95, and is a non-aromatic hydrocarbon, non-olefin, low-sulfur, low-Reid vapor pressure and high-octane alkane blending component. In addition, the boiling range of the alkylate is very wide, the alkylate meets the requirements of the gasoline with a new formula in many aspects, and the effect of the alkylate is increasingly obvious in the six or even more severe national oil standards of the future.
The current mainstream alkylation technology is; with liquid acid (HF or H)2SO4Ionic liquid), and the alkaline residue and acid residue generated in the production process can cause serious pollution to the environment due to the strong corrosivity and toxicity of acid. Solid acid alkylation technology is used as a new generation of environment-friendly alkylation technology, concentrated sulfuric acid is not used as a catalyst, platinum is used as an active carrier, an acid center is formed on the catalyst carrier to complete the carbon four alkylation reaction, and the catalyst is deactivated to realize online regeneration. The alkylate oil produced by the technology is a sulfur-free, olefin-free and aromatic hydrocarbon-free product, the Research Octane Number (RON) reaches more than 95, and the alkylate oil is a high-quality national V high-grade clean gasoline blending component.
Compared with the traditional sulfuric acid alkylation process, the solid acid alkylation process technology has the advantages that no waste oil or waste acid is generated in the production process, the pollution of acid oil and waste acid to the environment is thoroughly eliminated, and the safety problem caused by waste acid leakage is thoroughly solved, so that the process is a real green clean production process, and the subversive breakthrough of the technology in the global petrochemical industry is realized. Solid acid alkylation technology will be the trend for future alkylation technologies. However, the solid acid alkylation catalyst is expensive and has a severe requirement on raw materials, so that the method is very important for the pretreatment of the raw materials, and the perfection of the raw material pretreatment process directly determines the operation period of a solid acid alkylation device. In the actual production, the alkylation raw material mainly comprises ether and then has four carbon atoms and more impurities, the impurity content of the raw material far cannot meet the requirement of the catalyst, and severe raw material pretreatment is required. The common raw material pretreatment mostly adopts a purification device or exchange resin to remove substances harmful to the catalyst in the subsequent reaction, and because four components of carbon after the ether serving as the raw material are complex, the method can only remove one specific toxic component, and does not remove other components inhibiting the activity of the catalyst, so that the catalyst is seriously inactivated, the continuous regeneration cannot be further caused, the stability of continuous production is reduced, and the production cost is increased.
Therefore, how to find a pretreatment method for the post-carbon four of the raw material ether, reduce and remove harmful impurities, and ensure the continuous and stable operation of a solid acid alkylation device has become one of the problems to be solved by related production enterprises in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a pretreatment process and a pretreatment system for raw material carbon four, and in particular, to a pretreatment process and a pretreatment system for raw material carbon four for a solid acid alkylation process.
The invention provides a pretreatment process of raw material C4, which comprises the following steps:
1) washing and dehydrating the raw material C four to obtain a one-step processed product;
2) adsorbing the one-step treatment product obtained in the step to obtain a toxin-removed two-step treatment product;
3) carrying out hydrogenation operation on the two-step treated product obtained in the step, removing light hydrocarbon and oxygen-containing compounds, and carrying out comprehensive adsorption treatment to obtain a three-step treated product;
4) And (4) dehydrating the product obtained in the three steps again to obtain the pretreated raw material C4.
Preferably, the raw material C4 is the C4 after the ether;
the water washing is water washing methanol;
the temperature of the water washing is 0-50 ℃;
the pressure of the water washing is 1.1-1.7 MPa;
the methanol content in the washed raw material carbon four is less than or equal to 50 ppm.
Preferably, the dehydration mode is coalescence-separation type dehydration;
the dehydration temperature is 0-50 ℃;
the dehydration pressure is 1.1-1.8 MPa;
the flow rate of dehydration is less than or equal to 95% of the rated flow rate;
the water content in the dehydrated raw material carbon four is less than or equal to 10 ppm;
the step of drying is also included after the dehydration;
the drying mode is dehydration drying.
Preferably, the adsorption comprises adsorption desulfurization and adsorption dearsenification;
the adsorption desulfurization mode is to adopt a desulfurizing agent for adsorption desulfurization;
the temperature of the adsorption desulfurization is 0-50 ℃;
the pressure of the adsorption desulfurization is 0.8-1.6 MPa;
the sulfur content in the raw material carbon four after adsorption desulfurization is less than or equal to 1 ppm;
the adsorption dearsenization mode is to adopt dearsenization agent to adsorb dearsenization;
the temperature for adsorption dearsenization is 0-50 ℃;
The pressure for adsorbing and removing arsenic is 0.8-1.6 MPa;
the arsenic content in the raw material carbon four after adsorption and dearsenification is less than or equal to 1 ppm.
Preferably, the temperature of the hydrogenation operation is 50-150 ℃;
the pressure of the hydrogenation operation is 0.8-2.5 MPa;
the diene content in the raw material carbon four after the hydrogenation operation is less than or equal to 50 ppm;
the temperature for removing the light hydrocarbon and the oxygen-containing compound is 80-150 ℃;
the pressure for removing the light hydrocarbon and the oxygen-containing compound is 1.1-1.8 MPa;
the removal rate of the oxygen-containing compounds for removing the light hydrocarbon and the oxygen-containing compounds is more than or equal to 70 percent;
the comprehensive adsorption comprises one or more of adsorption and desorption of oxygen-containing compounds, adsorption and desorption of chlorides and adsorption and desorption of nitrides.
Preferably, the temperature of the comprehensive adsorption is 0-50 ℃;
the pressure of the comprehensive adsorption is 0.8-1.6 MPa;
the comprehensive adsorption comprises the steps of removing oxygen-containing compounds by adopting a deoxidizer, removing chlorides by adopting a dechlorinating agent and removing nitrides by adopting a denitrifier;
the content of oxygen-containing compounds in the comprehensively adsorbed raw material carbon four is less than or equal to 30ppmw, the content of chlorides is less than or equal to 1ppmw, and the content of nitrides is less than or equal to 1 ppmw.
Preferably, the step 3) may further include:
and (3) carrying out comprehensive adsorption treatment on the two-step treated product obtained in the step (1), then carrying out hydrogenation operation, and then removing light hydrocarbon and oxide to obtain a three-step treated product.
The invention provides a pretreatment system for raw material C4, which comprises:
washing the tower with water;
the coalescer is connected with the outlet of the water washing tower;
a dewatering dryer connected to the coalescer outlet;
the adsorber is connected with the outlet of the dehydration dryer;
the hydrogenation reactor is connected with the outlet of the adsorber;
the raw material lightness-removing tower is connected with the outlet of the hydrogenation reactor;
the comprehensive adsorber is connected with the outlet of the raw material lightness-removing tower;
a second coalescer connected to the outlet of the integrated adsorber.
Preferably, the water washing tower is a plate-type water washing tower;
the number of tower plates of the water washing tower is 30-80;
the coalescer is a vertical coalescer;
the filler of the dehydration dryer comprises ceramic balls and a molecular sieve;
the filler of the dehydration dryer is a multilayer filler;
the adsorber comprises a desulfurization adsorber connected with the outlet of the dehydration dryer and an arsenic removal adsorber connected with the outlet of the desulfurization adsorber.
Preferably, the filler of the hydrogenation reactor comprises ceramic balls, an isomerization catalyst and a protective agent;
a dechlorinating agent layer, a denitrogenation agent layer, a first deoxidizing agent layer and a second deoxidizing agent layer are arranged in the comprehensive adsorber;
the outlet of the adsorber is also connected with the inlet of the comprehensive adsorber;
the outlet of the comprehensive adsorber is also connected with the inlet of the hydrogenation reactor.
The invention provides a pretreatment process of a raw material C4, which comprises the following steps of firstly, washing and dehydrating the raw material C4 to obtain a one-step treatment product; then, adsorbing the one-step treatment product obtained in the step to obtain a second-step treatment product without toxin; then, carrying out hydrogenation reaction on the two-step treatment product obtained in the step, removing light hydrocarbon and oxygen-containing compounds, and carrying out comprehensive adsorption treatment to obtain a three-step treatment product; and finally, dehydrating the product obtained in the three steps again to obtain the pretreated raw material C4. Compared with the prior art, the invention aims at the defects that a plurality of toxic and harmful impurities exist in the existing ether rear carbon four, the impurity content of the raw material can not meet the requirement of the solid acid alkylation catalyst, and the common impurity removal means can only remove one specific toxic component and does not remove other components inhibiting the activity of the catalyst, so that the catalyst is seriously inactivated and can not be continuously regenerated when being used for the solid acid alkylation, the stability of continuous production is reduced, the production cost is increased, and the like.
The invention creatively provides a pretreatment process of raw material C4, which is a comprehensive pretreatment impurity removal process for the C4 after the ether treatment, particularly can effectively reduce and remove harmful impurities according to the requirements of a solid acid alkylation catalyst, can completely meet the requirements of the solid acid catalyst on raw material components, greatly improves the stability of continuous production, and also obviously reduces the production cost. The pretreatment process provided by the invention is simple and easy to control, corresponding pretreatment equipment does not use complex equipment which is difficult to popularize and has low yield, and the condition is mild, so that the method is particularly suitable for industrial popularization and application.
Experimental results show that according to the pretreatment process provided by the invention, the impurity content of the treated raw material C4 is greatly reduced or eliminated, and the requirements of the solid acid catalyst on raw material components can be completely met, wherein the impurity butadiene content is 0, the tert-butyl alcohol content is 0.05ppm, the MTBE content is 0, the methanol content is 0.11ppm, the sulfur content is 0.5ppm, the dimethyl ether content is 0.03ppm, the chlorine content is 0ppm, and the water content is 0.6 ppm.
Drawings
FIG. 1 is a simplified process flow diagram of the pretreatment process for carbon four, the feedstock for a solid acid alkylation process provided by the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts industrial purity or purity conventional in the field of solid acid alkylation preparation.
All the noun expressions and acronyms of the invention belong to the conventional noun expressions and acronyms in the field, each noun expression and acronym is clearly and definitely clear in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expressions and acronyms.
The invention provides a pretreatment process of raw material C4, which comprises the following steps:
1) washing and dehydrating the raw material C four to obtain a one-step processed product;
2) adsorbing the one-step treatment product obtained in the step to obtain a second-step treatment product without toxin;
3) Carrying out hydrogenation operation on the two-step treated product obtained in the step, removing light hydrocarbon and oxygen-containing compounds, and carrying out comprehensive adsorption treatment to obtain a three-step treated product;
4) and (4) dehydrating the product obtained in the three steps again to obtain the pretreated raw material C4.
The method comprises the steps of firstly washing and dehydrating the raw material C4 to obtain a one-step processed product.
The carbon four of the raw material is not particularly limited by the invention, the carbon four of the raw material is known by the skilled person, and mainly comprises n-butane and isobutane, the skilled person can select and adjust the carbon four according to the actual production situation, the raw material situation and the product requirement, the carbon four of the raw material is preferably carbon four after ether, namely carbon four after etherification reaction to remove isobutene, mainly butene-1, butane, cis-trans-butene-2 and the like, more preferably carbon four after ether used for the solid acid alkylation process, and the specific content can be seen in table 1. Table 1 shows the starting ether carbon number four, as conventionally used in solid acid alkylation processes.
TABLE 1
The process and parameters of the water washing are not particularly limited in the present invention, and the water washing process and parameters known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, raw material situation and product requirement, and the water washing in the present invention preferably refers to washing methanol, i.e. removing methanol by water washing. The temperature of the water washing is preferably 0-50 ℃, more preferably 10-40 ℃, and more preferably 20-30 ℃. The pressure of the water washing is preferably 1.1-1.7 MPa, more preferably 1.12-1.4 MPa, and more preferably 1.15-1.25 MPa.
In order to further improve the effect of the pretreatment and reduce the deactivation rate of the solid acid alkylation catalyst, the content of methanol in the washed raw material carbon four is preferably 50ppm or less, more preferably 40ppm or less, and still more preferably 30ppm or less.
The process and parameters of the dehydration are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the dehydration mode of the present invention is preferably coalescence-separation type dehydration. The dehydration temperature is preferably 0-50 ℃, more preferably 30-50 ℃, and more preferably 35-45 ℃. The pressure of the dehydration is preferably 1.1 to 1.8MPa, more preferably 1.1 to 1.7MPa, more preferably 1.12 to 1.4MPa, and more preferably 1.15 to 1.25 MPa. The flow rate of the dehydration is preferably 95% or less of the rated flow rate, more preferably 90% or less of the rated flow rate, and still more preferably 85% or less of the rated flow rate.
In the present invention, in order to further improve the effect of the pretreatment and reduce the deactivation rate of the solid acid alkylation catalyst, the water content in the dehydrated raw material carbon four is preferably 10ppm or less, more preferably 8ppm or less, and still more preferably 5ppm or less.
In order to further improve the pretreatment effect and reduce the deactivation rate of the solid acid alkylation catalyst, the invention integrates and refines the process, and preferably also comprises a drying step after dehydration. The drying method is not particularly limited in the present invention, and may be a drying method known to those skilled in the art, and those skilled in the art can select and adjust the drying method according to actual production conditions, raw material conditions and product requirements, and the drying method in the present invention is dehydration drying, that is, drying with a dehydration dryer. The drying parameters are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the drying temperature in the present invention is preferably 0 to 50 ℃, more preferably 10 to 40 ℃, and more preferably 30 to 50 ℃. The drying pressure is preferably 1.1-1.8 MPa, more preferably 1.3-1.6 MPa, and more preferably 1.45-1.55 MPa.
In the present invention, in order to further improve the effect of the pretreatment and reduce the deactivation rate of the solid acid alkylation catalyst, the water content in the dried raw material carbon four is preferably 1ppm or less, more preferably 0.8ppm or less, and still more preferably 0.5ppm or less.
The invention then obtains a second-step treatment product for removing toxin after the first-step treatment product obtained in the above step is subjected to adsorption treatment.
The present invention is not particularly limited to the specific process of the adsorption treatment, and the process of the adsorption treatment is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, raw material situation and product requirement, and the adsorption of the present invention preferably includes adsorption desulfurization and adsorption dearsenification.
The present invention has no particular limitation on the specific process and parameters of the adsorption desulfurization, and the process and parameters of the adsorption desulfurization known to those skilled in the art can be selected and adjusted according to the actual production situation, raw material situation and product requirement, and the adsorption desulfurization in the present invention is preferably performed by using a desulfurizing agent. The adsorption desulfurization temperature is preferably 0-50 ℃, more preferably 10-40 ℃, and more preferably 20-30 ℃. The pressure of the adsorption desulfurization is preferably 0.8-1.6 MPa, more preferably 0.85-1.3 MPa, and more preferably 0.9-1.1 MPa.
In order to further improve the effect of pretreatment and reduce the deactivation rate of the solid acid alkylation catalyst, the sulfur content in the raw material carbon four after adsorption desulfurization is preferably 1ppm or less, more preferably 0.8ppm or less, and still more preferably 0.5ppm or less.
The specific process and parameters of the adsorption dearsenification are not particularly limited in the invention, and the process and parameters of the adsorption dearsenification known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, raw material situation and product requirement, and the adsorption desulfurization mode of the invention is preferably to use dearsenification agent for adsorption dearsenification. The temperature for adsorption dearsenization is preferably 0-50 ℃, more preferably 10-40 ℃, and more preferably 20-30 ℃. The pressure for adsorbing and removing arsenic is preferably 0.8-1.6 MPa, more preferably 0.85-1.3 MPa, and more preferably 0.9-1.1 MPa.
In order to further improve the effect of pretreatment and reduce the deactivation rate of the solid acid alkylation catalyst, the content of arsenic in the raw material carbon four after adsorption and dearsenification is preferably not more than 1ppb, more preferably not more than 0.8ppb, and still more preferably not more than 0.5 ppb.
The two-step treated product obtained in the above steps is subjected to hydrogenation reaction, then light hydrocarbon and oxygen-containing compound are removed, and then the three-step treated product is obtained after comprehensive adsorption treatment.
The present invention has no particular limitation on the specific process and parameters of the hydrogenation reaction, and the process and parameters of the hydrogenation reaction well known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, the raw material situation and the product requirement, and the adsorption desulfurization method of the present invention is preferably to use dearsenization agent to adsorb dearsenization. The temperature of the hydrogenation reaction is preferably 50-150 ℃, more preferably 60-140 ℃, and more preferably 65-125 ℃. The pressure of the hydrogenation reaction is preferably 0.8-2.5 MPa, more preferably 1.0-2.3 MPa, and more preferably 1.45-2.05 MPa.
In the present invention, in order to further improve the effect of the pretreatment and reduce the deactivation rate of the solid acid alkylation catalyst, the content of diolefin in the raw material carbon four after the hydrogenation reaction is preferably not more than 50ppm, more preferably not more than 40ppm, and still more preferably not more than 30 ppm. The absorption rate of the monoolefin in the raw material carbon four in the hydrogenation reaction process is preferably 100%.
The specific process and parameters for removing the light hydrocarbon and the oxygen-containing compound are not particularly limited, and the process and parameters for removing the light hydrocarbon and the oxygen-containing compound known to the skilled in the art can be selected and adjusted by the skilled in the art according to the actual production condition, the raw material condition and the product requirement, and the temperature for removing the light hydrocarbon and the oxygen-containing compound is preferably 80-150 ℃, more preferably 90-140 ℃, and more preferably 100-120 ℃. The pressure for removing the light hydrocarbon and the oxygen-containing compound is preferably 1.1-1.8 MPa, more preferably 1.3-1.75 MPa, and more preferably 1.6-1.7 MPa.
In order to further improve the pretreatment effect and reduce the deactivation rate of the solid acid alkylation catalyst, the removal rate of the oxygen-containing compound of the raw material carbon four in the process of removing the light hydrocarbon and the oxygen-containing compound is preferably greater than or equal to 70%, more preferably greater than or equal to 75%, and more preferably greater than or equal to 80%.
The invention has no special limitation on the specific process and parameters of the comprehensive adsorption, and the process and parameters of the comprehensive adsorption are well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, the raw material situation and the product requirement, the comprehensive adsorption of the invention preferably comprises one or more of adsorption removal of oxygen-containing compounds, adsorption removal of chlorides and adsorption removal of nitrides, more preferably adsorption removal of oxygen-containing compounds, the adsorption removal of a plurality of chlorides and the adsorption removal of nitrides, more preferably the adsorption removal of a plurality of oxygen-containing compounds by a deoxidizer, the adsorption removal of chlorides by a dechlorinating agent and the adsorption removal of nitrides by a denitrifier, and most preferably the adsorption removal of oxygen-containing compounds by a deoxidizer, the adsorption removal of chlorides by a dechlorinating agent and the adsorption removal of nitrides by a denitrifier.
The oxygenate is not particularly limited in the present invention, and the oxygenate contained in the carbon four after the ether or the oxygenate possibly generated during the above treatment, which is well known to those skilled in the art, mainly includes DME and MTBE.
The comprehensive adsorption temperature is preferably 0-50 ℃, more preferably 10-40 ℃, and more preferably 20-30 ℃. The pressure of the comprehensive adsorption is preferably 0.8-1.6 MPa, more preferably 0.9-1.4 MPa, and more preferably 1.1-1.3 MPa.
In order to further improve the pretreatment effect and reduce the deactivation rate of the solid acid alkylation catalyst, the content of the oxygen-containing compound in the comprehensively adsorbed raw material carbon four is preferably less than or equal to 30ppmw, more preferably less than or equal to 25ppmw, and more preferably less than or equal to 20 ppmw; the content of chloride in the raw material carbon four after comprehensive adsorption is preferably less than or equal to 1ppmw, more preferably less than or equal to 0.8ppmw, and more preferably less than or equal to 0.5 ppmw; the content of the nitrides in the raw material carbonium after the comprehensive adsorption is preferably less than or equal to 1ppmw, more preferably less than or equal to 0.8ppmw, and more preferably less than or equal to 0.5 ppmw.
The process and parameters of the dehydration are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the dehydration mode of the present invention is preferably coalescence-separation type dehydration. The dehydration temperature is preferably 0-50 ℃, more preferably 10-45 ℃, and more preferably 20-40 ℃. The pressure of the dehydration is preferably 1.1-1.8 MPa, more preferably 1.1-1.7 MPa, more preferably 1.15-1.4 MPa, and more preferably 1.2-1.3 MPa. The flow rate of the dehydration is preferably 95% or less of the rated flow rate, more preferably 90% or less of the rated flow rate, and still more preferably 85% or less of the rated flow rate.
In order to further improve the pretreatment effect, reduce the deactivation rate of the solid acid alkylation catalyst, complete and refine the process, the step 3) can also be as follows:
and (3) carrying out comprehensive adsorption treatment on the two-step treated product obtained in the step (1), then carrying out hydrogenation reaction, and removing light hydrocarbon and oxides to obtain a three-step treated product.
The present invention has no particular limitation on the specific processes and parameters of the above-mentioned comprehensive adsorption treatment, and the process and parameters of comprehensive adsorption known to those skilled in the art can be selected and adjusted according to the actual production situation, raw material situation and product requirement, and the comprehensive adsorption of the present invention preferably comprises one or more of adsorption removal of oxygen-containing compounds, adsorption removal of chlorides and adsorption removal of nitrides, more preferably adsorption removal of oxygen-containing compounds, the adsorption removal of a plurality of chlorides and the adsorption removal of nitrides, more preferably the adsorption removal of a plurality of oxygen-containing compounds by a deoxidizer, the adsorption removal of chlorides by a dechlorinating agent and the adsorption removal of nitrides by a denitrifier, and most preferably the adsorption removal of oxygen-containing compounds by a deoxidizer, the adsorption removal of chlorides by a dechlorinating agent and the adsorption removal of nitrides by a denitrifier.
The temperature of the comprehensive adsorption is preferably 0-50 ℃, more preferably 10-40 ℃, and more preferably 20-30 ℃. The comprehensive adsorption pressure is preferably 0.8-1.6 MPa, more preferably 1.0-1.4 MPa, and more preferably 1.1-1.3 MPa.
In order to further improve the pretreatment effect, reduce the influence of oxygen-containing compounds, nitrides and chlorides in the raw material carbon four on the subsequent processes and reduce the deactivation rate of the solid acid alkylation catalyst, the content of the oxygen-containing compounds in the raw material carbon four after comprehensive adsorption treatment is preferably less than or equal to 30ppmw, more preferably less than or equal to 25ppmw and more preferably less than or equal to 20 ppmw; the content of chloride in the raw material carbon four after comprehensive adsorption is preferably less than or equal to 1ppmw, more preferably less than or equal to 0.8ppmw, and more preferably less than or equal to 0.5 ppmw; the content of the nitrides in the raw material carbonium after the comprehensive adsorption is preferably less than or equal to 1ppmw, more preferably less than or equal to 0.8ppmw, and more preferably less than or equal to 0.5 ppmw.
The process and parameters of the re-dewatering are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the re-dewatering mode of the present invention is preferably coalescence-separation type dewatering. The temperature of the secondary dehydration is preferably 0-50 ℃, more preferably 10-45 ℃, and more preferably 20-40 ℃. The pressure for the re-dehydration is preferably 1.1 to 1.8MPa, more preferably 1.1 to 1.7MPa, more preferably 1.15 to 1.4MPa, and more preferably 1.2 to 1.3 MPa. The flow rate of the re-dewatering is preferably 95% or less of the rated flow rate, more preferably 90% or less of the rated flow rate, and still more preferably 85% or less of the rated flow rate.
In the present invention, in order to further improve the effect of the pretreatment and reduce the deactivation rate of the solid acid alkylation catalyst, the water content in the raw material carbon four after the re-dehydration is preferably 10ppm or less, more preferably 8ppm or less, and still more preferably 5ppm or less.
Specifically, the pretreatment process of the raw material carbon four of the present invention can be as follows:
water washing methanol → coalescence dehydration → dry dehydration → adsorption desulfurization → adsorption dearsenification → hydrodediolefine → light dydrocarbon → comprehensive adsorption (deoxidation, chlorine and nitrogen) → coalescence dehydration → reaction system.
If the content of the oxygen-containing compound, chloride or nitride in the raw material is high, in order to ensure the requirement of the hydrogenation and diene removal catalyst on the raw material, the pretreatment process flow of the raw material C4 can be as follows: water washing methanol → coalescence dehydration → dry dehydration → adsorption desulfurization → adsorption dearsenification → comprehensive adsorption (deoxidation, chlorine and nitrogen) → hydrogenation and diene removal → light dydrocarbon removal → coalescence dehydration → reaction system.
The invention provides a pretreatment process of raw material C4, the raw material C4 is washed by a methanol washing process to remove methanol (less than 50ppm) in the raw material, enters a coalescence dehydration process to be dehydrated (less than 10ppm), enters a dehydration drying process to be further dehydrated and dried (less than 1ppm), then enters a desulfurization adsorption process with a desulfurizer to remove sulfur (less than 1ppm) in the raw material, the desulfurized raw material enters a dearsenization adsorption process with a dearsenization agent again to remove arsenic (less than 1ppb), the treated raw material meets the impurity requirement of a hydrogenation catalyst on the raw material, the raw material enters a hydrogenation reaction process for removing dialkene to remove dialkene (less than 50ppm), the hydrogenated raw material enters a lightness removing process to remove light hydrocarbon byproducts and most of oxides, and enters a comprehensive adsorption process with a deoxidizer, a dechlorination agent and a denitrifier one by one for oxide, The chloride and the nitride are adsorbed and removed, the removed raw materials enter a coalescence dehydration process again to remove water (less than 10ppm) generated by the hydrogenation reaction, and finally the qualified raw materials enter an alkylation reaction system for reaction.
The invention also provides a pretreatment system of the raw material carbon four, which comprises the following components:
washing the tower with water;
the coalescer is connected with the outlet of the water washing tower;
a dewatering dryer connected to the coalescer outlet;
the adsorber is connected with the outlet of the dehydration dryer;
the hydrogenation reactor is connected with the outlet of the adsorber;
the raw material lightness-removing tower is connected with the outlet of the hydrogenation reactor;
the comprehensive adsorber is connected with the outlet of the raw material lightness-removing tower;
a second coalescer connected to the outlet of the integrated adsorber.
The selection range and the optimization principle of the route and the parameters in the pretreatment system are consistent with those of the route and the parameters in the pretreatment process, and are not described in detail herein.
The connection mode is not particularly limited, and the connection mode known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the connection in the invention preferably means that the outlet of one device is connected with the inlet of another device, and the connection can be direct connection or connection through a device such as a pipeline.
The selection and parameters of the water washing tower are not particularly limited by the invention, and the water washing tower known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the water washing tower of the invention is preferably a plate type water washing tower, and more preferably a single overflow sieve plate tower. The number of the tower plates of the plate type water washing tower is preferably 30-80, more preferably 40-70, and more preferably 50-60.
The tower top temperature of the water washing tower is preferably 0-50 ℃, more preferably 10-40 ℃, more preferably 20-30 ℃, and the tower kettle temperature of the water washing tower is preferably 0-50 ℃, more preferably 10-40 ℃, more preferably 20-30 ℃. The top pressure of the water washing tower is preferably 1.1-1.7 MPa, more preferably 1.12-1.4 MPa, and more preferably 1.15-1.25 MPa. The pressure of the tower kettle of the water washing tower is preferably 1.45-1.65 MPa, more preferably 1.47-1.63 MPa, and more preferably 1.5-1.6 MPa.
The selection and parameters of the coalescer are not particularly limited by the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions, and product requirements, and the coalescer of the present invention is preferably a vertical coalescer. The filter element material of the coalescer is preferably polyester fiber.
The selection and parameters of the dewatering dryer are not particularly limited in the present invention, and the dewatering dryer known to those skilled in the art can be selected and adjusted according to actual production conditions, raw material conditions and product requirements, and the dewatering dryer of the present invention is preferably a packing type dewatering dryer, more preferably a packing type dewatering dryer including a plurality of layers of packing, and particularly may be a 2-layer packing. The filler of the dehydration dryer preferably comprises ceramic balls and a molecular sieve, and specifically can be ceramic balls, a 3A molecular sieve and a 13X molecular sieve.
The selection and parameters of the adsorber are not particularly limited, and those skilled in the art can select and adjust the adsorber according to actual production conditions, raw material conditions and product requirements, and the adsorber preferably comprises a desulfurization adsorber and a dearsenification adsorber, and more preferably sequentially comprises the desulfurization adsorber and the dearsenification adsorber, namely the desulfurization adsorber connected with the outlet of the dehydration dryer and the dearsenification adsorber connected with the outlet of the desulfurization adsorber.
The desulfurization adsorber of the invention is preferably a packed desulfurization adsorber, more preferably a packed desulfurization adsorber comprising a plurality of layers of packing, and particularly can be 2 layers of packing. The filler of the desulfurization adsorber preferably comprises ceramic balls and a desulfurizing agent. The arsenic removal adsorber of the invention is preferably a packing type arsenic removal adsorber, more preferably a packing type arsenic removal adsorber comprising a plurality of layers of packing, and particularly can be 2 layers of packing. The packing of the dearsenifying adsorber of the invention preferably comprises ceramic balls and a dearsenifying agent.
The selection and parameters of the hydrogenation reactor are not particularly limited in the present invention, and a hydrogenation reactor known to those skilled in the art may be used, and those skilled in the art may select and adjust the parameters according to actual production conditions, raw material conditions and product requirements, and the hydrogenation reactor of the present invention preferably uses a type II container, more preferably a packed hydrogenation reactor, and more preferably a packed hydrogenation reactor comprising a single layer or multiple layers of packing. The filler of the hydrogenation reactor of the present invention preferably comprises ceramic balls, an isomerization catalyst and a protective agent.
The selection and parameters of the integrated adsorber of the invention are not particularly limited, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the integrated adsorber of the invention is preferably a packed dehydration dryer, more preferably a packed integrated adsorber comprising multiple layers of packing, and may specifically be 3 layers of packing.
In order to further improve the pretreatment effect, reduce the deactivation rate of the solid acid alkylation catalyst, complete and refine the process, a dechlorinating agent and denitrogenating agent layer, a first deoxidizing agent layer and a second deoxidizing agent layer are preferably arranged in the comprehensive adsorber, and the dechlorinating agent and denitrogenating agent layer, the first deoxidizing agent layer and the second deoxidizing agent layer are preferably arranged in sequence along the feeding direction. The filler of the dechlorinating agent and the denitriding agent layer preferably comprises ceramic balls, the dechlorinating agent and the denitriding agent. The filler of the first deoxidizer layer preferably comprises ceramic balls and deoxidizer. The filler of the second deoxidizer layer preferably comprises ceramic balls and deoxidizer.
The selection and parameters of the second coalescer are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the second coalescer, preferably a vertical coalescer, according to the present invention. The filter element material of the second coalescer is preferably polyester fiber.
In order to further improve the pretreatment effect and reduce the deactivation rate of the solid acid alkylation catalyst, the invention integrates and refines the process, and the outlet of the adsorber is also connected with the inlet of the comprehensive adsorber corresponding to the optimized process route; the outlet of the comprehensive adsorber is also connected with the inlet of the hydrogenation reactor. When the content of the oxygen-containing compound, chloride or nitride in the raw material carbon four is high, the product of the two-step treatment can be treated by the comprehensive adsorber and then enters the subsequent hydrogenation reactor.
The steps of the invention provide a pretreatment system, in order to further improve the pretreatment effect, reduce the deactivation rate of the solid acid alkylation catalyst and complete and refine the process flow, specifically, the pretreatment system of the raw material carbon four can be as follows:
Firstly, the raw material carbon four-way pipe passes through a methanol washing tower to be in vapor-liquid contact with washing water, and methanol in the raw material is dissolved in the washing water, so that the methanol (less than 50ppm) in the raw material is removed.
Secondly, because the raw material is in vapor-liquid contact with water, the raw material coming out of the water washing tower has a certain amount of water, and the raw material enters a coalescence dehydrator for dehydration (less than 10ppm), and then enters a dehydration dryer for further dehydration and drying, thereby ensuring that the water content is not more than 1 ppm.
And thirdly, the dehydrated raw material enters a desulfurization adsorber with a desulfurizer, and the desulfurizer adsorbs sulfides (< 1ppm) in the raw material.
Fourthly, the raw material after desulfurization enters a dearsenization absorber with dearsenization agent again, and dearsenization is carried out through the dearsenization agent (less than 1 ppb).
Fifthly, removing impurities which affect the hydrogenation catalyst such as water, sulfur, arsenic and the like from the treated raw material to meet the requirement of the hydrogenation catalyst on the impurities of the raw material, pressurizing the raw material, then feeding the raw material into a hydrogenation reactor, hydrogenating and removing alkadiene (less than 50ppm) under the pressure of 1.5mpa, and keeping olefin.
Sixthly, the hydrogenated product has part of light hydrocarbon by-products, and enters a light hydrocarbon removing tower to remove the light hydrocarbon by-products and remove most of oxides.
And seventhly, the raw materials after removing the light hydrocarbon enter a comprehensive adsorption tower filled with a deoxidizing agent, a dechlorinating agent and a denitrifying agent again to adsorb and remove the oxides, the chlorides and the nitrides one by one. The integrated adsorber can be operated in double columns, with alternate adsorbers (1 adsorption, 1 regeneration for future use). The removed raw material enters a coalescent dehydrator again to remove water (less than 10ppm) generated by the hydrogenation reaction, and finally the qualified raw material enters an alkylation reaction system to react.
Referring to fig. 1, fig. 1 is a process flow diagram of a process for pretreating carbon four as a feedstock for a solid acid alkylation process according to the present invention.
Referring to table 2, table 2 shows the typical solid acid catalyst requirement for the feedstock carbon four after the ether. TABLE 2
The invention provides a pretreatment process and a pretreatment system for raw material ether rear carbon four, and particularly fills a deoxidizer, a dechlorinating agent and a denitrifier in a container in a layered grading manner, thereby not only ensuring the adsorption effect, but also saving the equipment investment and the occupied area. After hydrogenation and diene removal, a light hydrocarbon removal tower is arranged, light hydrocarbon and more than 70% of oxides can be removed simultaneously by the light hydrocarbon removal tower, and the service cycle of the deoxidizer of the subsequent comprehensive absorber can be prolonged by more than 3 times; more particularly, a protective measure (methanol removal → coalescence dehydration → drying dehydration → desulfurization → dearsenification) is set before the hydrogenation and the diene removal, so that the activity of the catalyst (noble metal) for hydrogenation and diene removal is effectively prevented from being influenced in the pretreatment process. In addition, a coalescent dehydrator is arranged at the end of the whole raw material pretreatment process, so that the influence of water to a back-path alkylation reactor caused by the steam regeneration switching misoperation or fault of the previous comprehensive adsorber is effectively prevented. The invention can effectively reduce and remove harmful impurities aiming at the requirements of the solid acid alkylation catalyst, can completely meet the requirements of the solid acid catalyst on raw material components, greatly improves the stability of continuous production, and also obviously reduces the production cost. The pretreatment process provided by the invention is simple and easy to control, corresponding pretreatment equipment does not use complex equipment which is difficult to popularize and has low yield, and the condition is mild, so that the method is particularly suitable for industrial popularization and application.
Experimental results show that according to the pretreatment process provided by the invention, the impurity content of the treated raw material C4 is greatly reduced or eliminated, and the requirements of the solid acid catalyst on raw material components can be completely met, wherein the impurity butadiene content is 0, the tert-butyl alcohol content is 0.05ppm, the MTBE content is 0, the methanol content is 0.11ppm, the sulfur content is 0.5ppm, the dimethyl ether content is 0.03ppm, the chlorine content is 0ppm, and the water content is 0.6 ppm.
For further illustration of the present invention, the following will describe in detail a pretreatment process and a pretreatment system for raw material carbon four according to the present invention with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
1 ingredient of raw Material
See table 1 for alkylation feed C including: 0.04% of propane; 34.56% of isobutane; n-butane 11.8% pentane 0; 14.05 percent of 1-butene; 0.14 percent of isobutene; 15.38 percent of cis-2-butene; butadiene 0; 1.1% of tert-butyl alcohol; 0.47% of MTBE; 2.83 percent of methanol; 15.9ppm of sulfur; dimethyl ether 0; chlorine was 0, As content 10ppb, water 2.3 ppm.
2 treatment process
Firstly, the raw material carbon four-way is in vapor-liquid contact with washing water through a methanol washing tower, and the methanol in the raw material is dissolved in the washing water, so that the methanol in the raw material is removed (less than 50 ppm).
Wherein the water washing tower is a single overflow sieve plate tower, the number of the tower plates is 69, the temperature of the top of the water washing tower is 30 ℃, the pressure of the top of the water washing tower is 1.15MPa, the temperature of the kettle of the water washing tower is 25 ℃, the pressure of the kettle of the water washing tower is 1.22MPa,
secondly, because the raw material is in vapor-liquid contact with water, the raw material coming out of the water washing tower has a certain amount of water, and the raw material enters a coalescence dehydrator for dehydration (less than 10ppm), and then enters a dehydration dryer for further dehydration and drying, thereby ensuring that the water content is not more than 1 ppm.
Wherein the dehydration temperature is 30 ℃, and the dehydration pressure is 1.1 MPa.
Thirdly, the dehydrated raw material enters a desulfurization adsorber with a desulfurizing agent, and the desulfurizing agent adsorbs sulfide (less than 1ppm) in the raw material.
Wherein the temperature of desulfurization is 25 ℃, and the pressure of desulfurization is 0.9 MPa.
Fourthly, the desulfurized raw material enters the dearsenization adsorber with the dearsenization agent again, and the dearsenization is carried out through the dearsenization agent (less than 1 ppm).
Wherein the temperature for dearsenization is 25 ℃, and the pressure for dearsenization is 0.9 MPa.
Fifthly, removing impurities which affect the hydrogenation catalyst such as water, sulfur, arsenic and the like from the treated raw material to meet the requirement of the hydrogenation catalyst on the impurities of the raw material, adding the raw material into a hydrogenation reactor after the pressure of the raw material is increased, and removing alkadiene (< 50ppm) by hydrogenation under the pressure of 1.5mpa and keeping olefin.
Wherein the temperature of the hydrogenation operation is 53 ℃, and the pressure of the hydrogenation operation is 1.95 MPa.
Sixthly, the hydrogenated product has partial light hydrocarbon by-product, and enters a light hydrocarbon removing tower to remove the light hydrocarbon by-product and also remove most of the oxide.
Wherein the temperature for removing the light hydrocarbon and the oxygen-containing compound is 103 ℃, and the pressure for removing the light hydrocarbon and the oxygen-containing compound is 1.67 MPa.
And seventhly, the raw materials after removing the light hydrocarbon enter a comprehensive adsorption tower filled with a deoxidizer, a dechlorinating agent and a denitrifier to adsorb and remove the oxide, the chloride and the nitride one by one. The integrated adsorber can be operated in double columns, with alternate adsorbers (1 adsorption, 1 regeneration for future use).
Wherein, the comprehensive adsorber is sequentially provided with a dechlorinating agent layer, a denitrogenation agent layer, a first deoxidizing agent layer and a second deoxidizing agent layer along the feeding direction. The temperature of comprehensive adsorption is 25 ℃, and the pressure of comprehensive adsorption is 1.0 MPa.
The removed raw material enters a coalescence dehydrator again to remove water (less than 10ppm) generated by the hydrogenation reaction, and finally the qualified raw material enters an alkylation reaction system to react.
The results of the detection of the ether-carbon-four of the pretreated raw material in example 1 of the present invention show that the pretreated raw material contains 0 butadiene, 0 tert-butyl alcohol, 0 MTBE, 0 methanol, 0.43ppm sulfur, 0 dimethyl ether, 0 chlorine, 0 water, 0.6ppm heavy metal.
Example 2
1 ingredient of raw Material
See table 1 for alkylation feed a including: 0.02% of propane; 51.08% of isobutane; 8.73 percent of n-butane; pentane 0; 0% of 1-butene; 0.01 percent of isobutene; 11.09% of cis-2-butene; 18.88 percent of fumaric; butadiene 0; 0 of tert-butyl alcohol; 8.58% of MTBE; 1.7 percent of methanol; 21.8ppm of sulfur; dimethyl ether 0; chlorine is 0 and water is 0.8 ppm.
2 treatment process
Firstly, the raw material carbon four-way is in vapor-liquid contact with washing water through a methanol washing tower, and the methanol in the raw material is dissolved in the washing water, so that the methanol in the raw material is removed (less than 50 ppm).
Wherein the water washing tower is a single overflow sieve plate tower, the number of the tower plates is 69, the temperature of the top of the water washing tower is 31 ℃, the pressure of the top of the water washing tower is 1.16MPa, the temperature of the bottom of the water washing tower is 26 ℃, the pressure of the bottom of the water washing tower is 1.24MPa,
secondly, because the raw material is in vapor-liquid contact with water, the raw material coming out of the water washing tower contains a certain amount of water, and the raw material enters a coalescence dehydrator for dehydration (less than 10ppm), and then enters a dehydration dryer for further dehydration and drying, so that the water content is not more than 1 ppm.
Wherein the dehydration temperature is 31 ℃, and the dehydration pressure is 1.12 MPa.
Thirdly, the dehydrated raw material enters a desulfurization adsorber with a desulfurizing agent, and the desulfurizing agent adsorbs sulfide (less than 1ppm) in the raw material.
Wherein the temperature of desulfurization is 26 ℃, and the pressure of desulfurization is 0.92 MPa.
Fourthly, the desulfurized raw material enters the dearsenization adsorber with the dearsenization agent again, and the dearsenization is carried out through the dearsenization agent (less than 1 ppm).
Wherein the temperature for dearsenization is 25.5 ℃, and the pressure for dearsenization is 0.91 MPa.
Fifthly, removing impurities which affect the hydrogenation catalyst such as water, sulfur, arsenic and the like from the treated raw material to meet the requirement of the hydrogenation catalyst on the impurities of the raw material, adding the raw material into a hydrogenation reactor after the pressure of the raw material is increased, and removing alkadiene (< 50ppm) by hydrogenation under the pressure of 1.5mpa and keeping olefin.
Wherein the temperature of the hydrogenation operation is 54 ℃, and the pressure of the hydrogenation operation is 1.96 MPa.
Sixthly, the hydrogenated product has partial light hydrocarbon by-product, and enters a light hydrocarbon removing tower to remove the light hydrocarbon by-product and also remove most of the oxide.
Wherein the temperature for removing the light hydrocarbon and the oxygen-containing compound is 104 ℃, and the pressure for removing the light hydrocarbon and the oxygen-containing compound is 1.68 MPa.
And seventhly, the raw materials after removing the light hydrocarbon enter a comprehensive adsorption tower filled with a deoxidizer, a dechlorinating agent and a denitrifier to adsorb and remove the oxide, the chloride and the nitride one by one. The integrated adsorber can be operated in double columns, switching adsorption from one to the other (1 adsorption, 1 regeneration for use).
Wherein, the comprehensive adsorber is provided with a dechlorinating agent layer, a denitrogenation agent layer, a first deoxidizing agent layer and a second deoxidizing agent layer in sequence along the feeding direction. The temperature of the comprehensive adsorption is 26 ℃, and the pressure of the comprehensive adsorption is 1.1 MPa.
The removed raw material enters a coalescence dehydrator again to remove water (less than 10ppm) generated by the hydrogenation reaction, and finally the qualified raw material enters an alkylation reaction system to react.
The results of the detection of the ether-carbon-four of the pretreated raw material obtained in example 2 of the present invention show that the pretreated raw material contains 0 butadiene, 0 tert-butyl alcohol, 0 MTBE, 0 methanol, 0.43ppm sulfur, 0 dimethyl ether, 0 chlorine, 0 water, 0.6ppm and 0 heavy metal.
Example 3
1 ingredient of raw Material
See table 1 for alkylation feed B including: 0.01% of propane; isobutane 41.38%; n-butane 10.81%; pentane 0; 1-butene 0; 0.01 percent of isobutene; 14.21% of cis-2-butene; 20.35 percent of fumaric; butadiene 0; 0.57 of tert-butyl alcohol; MTBE 0; 2.53 percent of methanol; 20.9ppm of sulfur; dimethyl ether 0.91; 0.8ppm of water; also included are 0.9ppm chlorine and 1.0ppm nitrogen.
2 treatment process
Firstly, impurities which affect a hydrogenation catalyst such as water, sulfur, arsenic and the like are removed from the treated raw material, the requirement of the hydrogenation catalyst on the impurities of the raw material is met, the maximum allowable concentration of chlorine of the hydrogenation catalyst is less than 0.5ppm and nitrogen is less than 1ppm, and therefore, chlorine and nitrogen are removed before the raw material enters a hydrogenation reactor. At the moment, the process requires that chlorine and nitrogen are firstly absorbed in a comprehensive absorber. The obtained product enters a comprehensive adsorption tower filled with a deoxidizer, a dechlorinating agent and a denitrifier to adsorb and remove oxides, chlorides and nitrides one by one. The integrated adsorber can be operated in double columns, with alternate adsorbers (1 adsorption, 1 regeneration for future use).
Wherein, the comprehensive adsorber is provided with a dechlorinating agent layer, a denitrogenation agent layer, a first deoxidizing agent layer and a second deoxidizing agent layer in sequence along the feeding direction. The temperature of the comprehensive adsorption is 26.5 ℃, and the pressure of the comprehensive adsorption is 1.15 MPa.
The requirement is that the feedstock is fed to the hydrogenation reactor after being pressurized, and is hydrogenated to remove diolefins (< 50ppm) and to retain olefins at a pressure of 1.5 mpa.
Wherein the temperature of the hydrogenation operation is 55 ℃, and the pressure of the hydrogenation operation is 1.99 MPa.
Secondly, the hydrogenated product has partial light hydrocarbon byproducts, and the light hydrocarbon byproducts and most oxides are removed in a light hydrocarbon removal tower.
Wherein the temperature for removing the light hydrocarbon and the oxygen-containing compound is 103.5 ℃, and the pressure for removing the light hydrocarbon and the oxygen-containing compound is 1.64 MPa.
Thirdly, the raw material without light hydrocarbon enters a coalescent dehydrator again to remove water (less than 10ppm) generated by hydrogenation reaction, and finally the raw material which is qualified enters an alkylation reaction system to react.
The detection of the carbon number four after the raw material ether is carried out before the pre-hydrogenation reactor in the embodiment 3 of the invention, and the detection of the carbon number four after the pre-treated raw material ether is carried out, the result shows that: the chlorine content was 0.01ppm and the nitrogen content was 0.05 ppm. In the pretreated raw material, the butadiene content was 0, the tert-butanol content was 0, the MTBE content was 0, the methanol content was 0.23ppm, the sulfur content was 0.2ppm, the dimethyl ether content was 0, the chlorine content was 0.01ppm, the nitrogen content was 0.05ppm, the water content was 0.6ppm, and the heavy metal content was 0.
The foregoing detailed description of the process and system for pretreating carbon four, a feedstock for solid acid alkylation processes, provided by the present invention, and the principles and embodiments of the present invention are described herein using specific examples, which are intended to facilitate an understanding of the process and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (9)
1. The pretreatment process of the raw material C4 is characterized by comprising the following steps of:
1) washing and dehydrating the raw material C four to obtain a one-step processed product;
2) adsorbing the one-step treatment product obtained in the step to obtain a toxin-removed two-step treatment product;
the adsorption comprises adsorption desulfurization and adsorption dearsenification;
3) carrying out hydrogenation operation on the two-step treated product obtained in the step, removing light hydrocarbon and oxygen-containing compounds, and carrying out comprehensive adsorption treatment to obtain a three-step treated product;
the comprehensive adsorption comprises the steps of adsorbing and removing oxygen-containing compounds, adsorbing and removing chlorides and adsorbing and removing nitrides;
4) and (4) dehydrating the product obtained in the three steps again to obtain the pretreated raw material C4.
2. The pretreatment process of claim 1, wherein the feedstock C.sub.D is an ethereal C.sub.D;
the water washing is water washing methanol;
the temperature of the water washing is 0-50 ℃;
the pressure of the water washing is 1.1-1.7 MPa;
the methanol content in the washed raw material carbon four is less than or equal to 50 ppm.
3. The pretreatment process of claim 1, wherein the dehydration is by coalescence-separation dehydration;
The dehydration temperature is 0-50 ℃;
the dehydration pressure is 1.1-1.8 MPa;
the flow rate of dehydration is less than or equal to 95% of the rated flow rate;
the water content in the dehydrated raw material carbon four is less than or equal to 10 ppm;
the step of drying is also included after the dehydration;
the drying mode is dehydration drying.
4. The pretreatment process according to claim 1, wherein the adsorption desulfurization is performed by using a desulfurizing agent;
the temperature of the adsorption desulfurization is 0-50 ℃;
the pressure of the adsorption desulfurization is 0.8-1.6 MPa;
the sulfur content in the raw material carbon four after adsorption desulfurization is less than or equal to 1 ppm;
the adsorption dearsenization mode is to adopt dearsenization agent to adsorb dearsenization;
the temperature for adsorption dearsenization is 0-50 ℃;
the pressure for adsorbing and removing arsenic is 0.8-1.6 MPa;
the arsenic content in the raw material carbon four after adsorption and dearsenification is less than or equal to 1 ppm.
5. The pretreatment process according to claim 1, wherein the hydroprocessing temperature is 50 to 150 ℃;
the pressure of the hydrogenation operation is 0.8-2.5 MPa;
the diene content in the raw material carbon four after the hydrogenation operation is less than or equal to 50 ppm;
the temperature for removing light hydrocarbon and oxygen-containing compounds is 80-150 ℃;
The pressure for removing the light hydrocarbon and the oxygen-containing compound is 1.1-1.8 MPa;
the removal rate of the oxygen-containing compounds for removing the light hydrocarbon and the oxygen-containing compounds is more than or equal to 70 percent.
6. The pretreatment process according to claim 5, wherein the temperature of the comprehensive adsorption is 0-50 ℃;
the pressure of the comprehensive adsorption is 0.8-1.6 MPa;
the comprehensive adsorption comprises the steps of removing oxygen-containing compounds by adopting a deoxidizer, removing chlorides by adopting a dechlorinating agent and removing nitrides by adopting a denitrifier;
the content of oxygen-containing compounds in the comprehensively adsorbed raw material carbon four is less than or equal to 30ppmw, the content of chlorides is less than or equal to 1ppmw, and the content of nitrides is less than or equal to 1 ppmw.
7. A pretreatment system for raw material C4, comprising:
washing the tower with water;
the coalescer is connected with the outlet of the water washing tower;
a dewatering dryer connected to the coalescer outlet;
the adsorber is connected with the outlet of the dehydration dryer;
the hydrogenation reactor is connected with the outlet of the adsorber;
the raw material lightness-removing tower is connected with the outlet of the hydrogenation reactor;
the comprehensive adsorber is connected with the outlet of the raw material lightness-removing tower;
a second coalescer connected to the outlet of the integrated adsorber;
The comprehensive adsorber is provided with a dechlorinating agent layer, a denitriding agent layer, a first deoxidizing agent layer and a second deoxidizing agent layer.
8. The pretreatment system of claim 7, wherein the water wash column is a tray water wash column;
the number of tower plates of the water washing tower is 30-80;
the coalescer is a vertical coalescer;
the filler of the dehydration dryer comprises ceramic balls and a molecular sieve;
the filler of the dehydration dryer is a multilayer filler;
the adsorber comprises a desulfurization adsorber connected with the outlet of the dehydration dryer and an arsenic removal adsorber connected with the outlet of the desulfurization adsorber.
9. The pretreatment system of claim 7, wherein the packing of the hydrogenation reactor comprises ceramic balls, an isomerization catalyst, and a protective agent; the outlet of the adsorber is also connected with the inlet of the comprehensive adsorber;
the outlet of the comprehensive adsorber is also connected with the inlet of the hydrogenation reactor.
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| CN1639089A (en) * | 2002-02-28 | 2005-07-13 | 斯东及韦伯斯特公司 | Production of alkyl aromatic compounds |
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| CN1639089A (en) * | 2002-02-28 | 2005-07-13 | 斯东及韦伯斯特公司 | Production of alkyl aromatic compounds |
| CN105152840A (en) * | 2015-09-14 | 2015-12-16 | 中国成达工程有限公司 | Process for refining C-4 hydrocarbon fluid |
| CN105601460A (en) * | 2015-12-21 | 2016-05-25 | 中国石油大学(北京) | Refining method of alkylation feedstock |
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