CN108530580B - Process gas deep processing method for preparing olefin from methanol - Google Patents
Process gas deep processing method for preparing olefin from methanol Download PDFInfo
- Publication number
- CN108530580B CN108530580B CN201810350615.5A CN201810350615A CN108530580B CN 108530580 B CN108530580 B CN 108530580B CN 201810350615 A CN201810350615 A CN 201810350615A CN 108530580 B CN108530580 B CN 108530580B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- condition
- propylene
- mass
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/18—Preparation of carboxylic acid nitriles by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process gas deep processing method for preparing olefin from methanol, which mainly comprises the following steps: firstly, separating ethylene, propylene I, butylene and a small amount of butadiene from process gas prepared by methanol through a catalyst 1 through a separating device; reacting ethylene and butylene through a catalyst 2 to generate propylene II; thirdly, propylene reacts through a catalyst 3 to generate acrylonitrile; fourthly, butadiene and acrylonitrile are generated into nitrile rubber by a catalyst 4; fifthly, the nitrile rubber is generated into hydrogenated nitrile rubber by a catalyst 5. The method carries out process route design aiming at the proportion of ethylene, propylene, butylene and a small amount of butadiene in a process gas product, and the hydrogenated nitrile rubber generated by the reaction has high yield and high added value. The invention can reduce the production cost, is green and environment-friendly, has high automation degree and is convenient for industrial popularization.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to the field of deep processing of process gas for preparing olefin from methanol.
Background
Hydrogenated nitrile rubber, abbreviation: HNBR, or H-NBR. Is a new product of nitrile butadiene rubber (NBR for short). Hydrogenated nitrile rubber (HNBR) is a highly saturated elastomer obtained by the specific hydrotreatment of nitrile rubber. The hydrogenated nitrile rubber has good oil resistance (good resistance to fuel oil, lubricating oil and aromatic solvents); and because of its highly saturated structure, make it have good heat resistance, fine chemical resistance (to freon, acid, alkali have good resistance), excellent ozone resistance, higher compression set resistance; meanwhile, the hydrogenated nitrile rubber has the characteristics of high strength, high tearing property, excellent wear resistance and the like, and is one of rubbers with extremely excellent comprehensive properties. Hydrogenated nitrile rubbers are widely used in the oil field, automotive industry, etc. The Raynaud company is a major supplier of hydrogenated nitrile rubber raw materials, and has a great experience in the fields of hydrogenated nitrile rubber formulation and processing. According to different application fields, the rubber compound product with complete variety, excellent performance and stable quality, various hydrogenated nitrile rubber plates and molded products can be professionally provided.
With the development of the automobile and petroleum industries, rubber parts are required to have good properties of heat resistance, high temperature resistance, high pressure resistance, oxygen resistance and the like in addition to oil resistance. Conventional nitrile rubber (NBR) has been far from meeting these requirements, and although some of these uses have been replaced by fluororubbers, fluororubbers are expensive. Thus, improvements in NBR properties have been sought and hydrogenated nitrile rubbers have been successfully developed to meet this new need.
The catalyst developed by the engineering Limited company of Tianchen in China for preparing olefin from methanol is mainly a silicon-aluminium-phosphorus molecular sieve which can lead the conversion rate of methanol to reach 100 percent or approach 100 percent, lead the selectivity of ethylene and propylene to be more than 78 percent and hardly have C5The product, the outstanding hydrothermal stability and the proper pore channel structure of the silicon-aluminum-phosphorus molecular sieve enable the performance of the silicon-aluminum-phosphorus molecular sieve to be more excellent, and the silicon-aluminum-phosphorus molecular sieve can be widely applied in the future.
At present, the international research on how to deeply process the methanol-to-olefin products so as to obtain more output value and benefits, promote the extension of product chains and the diversified development of products so as to enhance benefits and promote the development of the field is a popular option for the research in the field at present.
Disclosure of Invention
In view of this, the present invention aims to provide a method for further processing a process gas for preparing olefins from methanol, which can improve the economic output value of the process gas.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for deep processing of process gas for preparing olefin from methanol comprises the following steps:
step1, under the condition of setting the condition 1, separating ethylene, propylene I, butylene, butadiene and other impurity gases from the process gas prepared by the methanol through the catalyst 1 through a separating device, wherein the mass fraction of the process gas is as follows: 30-43% of ethylene, 78-44% of propylene I35, 10-15% of butene, 2-8% of butadiene and 5-7% of other impurity gases; other contaminant gases include from methane, ethane to carbon ten, and so forth.
Step 2: under the condition of setting the condition 2, ethylene and butylene react through a catalyst 2 to generate propylene II which is 30-60% of the mass of the ethylene;
step 3: propylene I separated from Step1 and propylene II prepared from Step2 are added and mixed to form propylene, and under the condition of setting the condition 3, the propylene reacts with ammonia gas with the molar ratio of 1.1-1.2 times that of the propylene, air with the molar ratio of 2.0-3.0 times that of the propylene and water vapor with the molar ratio of 2.7-3.2 times that of the propylene through a catalyst 3 to generate 65-77% of acrylonitrile corresponding to the mass of the propylene;
step 4: under the condition of setting the condition 4, butadiene separated in Step1 and 4-8 times of butadiene are added to generate acrylonitrile-butadiene rubber with acrylonitrile generated in Step3 through a catalyst 4;
step 5: under the condition 5, the nitrile rubber is dissolved in an organic solvent and then hydrogenated nitrile rubber is produced by the catalyst 5.
Preferably, the catalyst 1 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 2-10 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.01-0.1 time of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 1-4 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 2-6 times of the mass of the silicon-aluminum-phosphorus molecular; the catalyst 2 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 1-8 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.05-0.2 time of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 2-6 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 1-4 times of the mass of the silicon-aluminum-; the catalyst 3 is one or a mixture of two or more of catalysts which take coarse-pore silica gel as a carrier to load oxides of heavy metals such as antimony, bismuth, vanadium, tungsten, iron, cobalt and nickel; the catalyst 4 refers to a catalyst in which hydrogen peroxide and ferrous salt coexist; the catalyst 5 is a palladium or rhodium catalyst.
Preferably, the condition 1 is set as that the reaction temperature is 400-470 ℃, and the reaction pressure is 0-1.1MPa in the circulating fluidized bed; setting the condition 2 to be a circulating fluidized bed with the reaction temperature of 420-500 ℃ and the reaction pressure of 0-0.7 MPa; the set condition 3 is that the reaction temperature is 400-; setting the condition 4 to be 5-30 ℃ and 0-1.0 MPa; the set condition 5 means that the reaction temperature is 20-60 ℃ and the reaction pressure is 0.5-5 MPa.
Preferably, the mass fraction of the methanol for treatment is 90-99%, wherein the content of impurity iron is less than 80 ppm.
Preferably, conditions 1 and 2 are set to use high purity nitrogen as a carrier gas.
Preferably, the butylene is a mixture of n-butylene, isobutylene, cis-2-butylene and trans-2-butylene, wherein the mass fraction of isobutylene in the mixture is 5-10%.
Preferably, in the set condition 5, the mass of the added catalyst 5 is 0.5-1% of that of the nitrile rubber, and the organic solvent for dissolving the nitrile rubber is one or two of benzene, chlorobenzene, pyridine and acetone.
Preferably, the setting condition 4 further comprises a polymerization degree increasing regulator alkyl mercaptan, an emulsifier, an electrolyte and a polymerization terminator.
Preferably, the emulsifier is abietic acid soap or fatty acid soap, the electrolyte is potassium chloride, sodium phosphate or sodium sulfate, and the polymerization terminator is hydroquinone.
Compared with the prior art, the method has the advantages that the process route design is carried out on the ratio of ethylene, propylene, butylene and a small amount of butadiene in the process gas combined process gas product, and the hydrogenated nitrile rubber generated by the reaction has high yield and high added value. The invention can reduce the production cost, is green and environment-friendly, has high automation degree and is convenient for industrial popularization.
Drawings
FIG. 1 is a schematic diagram of a process flow of a process gas deep processing method for preparing olefins from methanol according to an embodiment of the present invention;
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention is described in detail below with reference to the following example and fig. 1.
Example 1
A method for deep processing of process gas for preparing olefin from methanol comprises the following steps:
step1, under the condition of setting the condition 1, separating ethylene, propylene I, butylene, butadiene and other impurity gases from the process gas prepared by the methanol through the catalyst 1 through a separating device, wherein the mass fraction of the process gas is as follows: 33% of ethylene, 39% of propylene I, 13% of butylene, 8% of butadiene and 7% of other impurity gases; other contaminant gases include from methane, ethane to carbon ten, and so forth.
Step 2: under the condition 2, ethylene and butylene react through the catalyst 2 to generate propylene II which is 40 percent of the mass of the ethylene;
step 3: propylene I separated in Step1 and propylene II prepared in Step2 are added and mixed to form propylene, and under the condition of setting the condition 3, the propylene reacts with ammonia gas with the molar ratio of 1.1 times that of the propylene, air with the molar ratio of 2.0 times that of the propylene and water vapor with the molar ratio of 2.7 times that of the propylene through a catalyst 3 to generate 68% of acrylonitrile corresponding to the mass of the propylene;
step 4: under the condition of setting the condition 4, the butadiene separated in the Step1 and 4 times of the butadiene are added to generate acrylonitrile-butadiene rubber with acrylonitrile generated in the Step3 through the catalyst 4;
step 5: under the condition 5, the nitrile rubber is dissolved in an organic solvent and then hydrogenated nitrile rubber is produced by the catalyst 5.
The catalyst 1 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 3 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.02 time of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 1 time of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 2 times of the mass of the silicon-aluminum-phosphorus; the catalyst 2 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 4 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.05 times of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 2 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 1 time of the mass of the silicon-aluminum-; the catalyst 3 is a mixture of a catalyst which takes coarse silica gel as a carrier and is loaded with antimony oxide and a catalyst which is loaded with bismuth oxide; the catalyst 4 refers to a catalyst in which hydrogen peroxide and ferrous nitrate coexist; the catalyst 5 is a palladium catalyst.
Setting the condition 1 refers to that the reaction temperature is 400 ℃, and the reaction pressure is 0.2MPa in the circulating fluidized bed; setting the condition 2 refers to that the reaction temperature is 420 ℃, and the reaction pressure is 0.3MPa in the circulating fluidized bed; setting the condition 3 to be that the reaction temperature is 420 ℃ and the reaction pressure is 0.1 MPa; setting the condition 4 means that the reaction temperature is 5 ℃ and the reaction pressure is 0.2 MPa; the set condition 5 means that the reaction temperature was 20 ℃ and the reaction pressure was 0.5 MPa.
The mass fraction of the methanol for treatment accounts for 90 percent, wherein the content of impurity iron is lower than 80 ppm.
Conditions 1 and 2 were set using high purity nitrogen as a carrier gas.
The butene is a mixture of n-butene, isobutene, cis-2-butene and trans-2-butene, wherein the mass fraction of the isobutene in the mixture is 5%.
In the set condition 5, the mass of the added catalyst 5 is 0.5% of that of the nitrile rubber, and the organic solvent for dissolving the nitrile rubber is benzene.
The setting condition 4 further includes a polymerization degree increasing regulator alkyl mercaptan, an emulsifier, an electrolyte and a polymerization terminator. The emulsifier is rosin acid soap, the electrolyte is potassium chloride, and the polymerization terminator is hydroquinone.
Example 2
A method for deep processing of process gas for preparing olefin from methanol comprises the following steps:
step1, under the condition of setting the condition 1, separating ethylene, propylene I, butylene, butadiene and other impurity gases from the process gas prepared by the methanol through the catalyst 1 through a separating device, wherein the mass fraction of the process gas is as follows: 40% of ethylene, 8% of propylene I35%, 12% of butylene, 8% of butadiene and 5% of other impurity gases; other contaminant gases include from methane, ethane to carbon ten, and so forth.
Step 2: under the condition 2, ethylene and butylene react through a catalyst 2 to generate propylene II which is equivalent to 60 percent of the mass of the ethylene;
step 3: propylene I separated in Step1 and propylene II prepared in Step2 are added and mixed to form propylene, and under the condition of setting the condition 3, the propylene reacts with ammonia gas with the molar ratio of 1.2 times that of the propylene, air with the molar ratio of 3.0 times that of the propylene and water vapor with the molar ratio of 3.2 times that of the propylene through a catalyst 3 to generate 77 percent of acrylonitrile corresponding to the mass of the propylene;
step 4: under the condition of setting the condition 4, the butadiene separated in the Step1 and 8 times of the butadiene are added to generate acrylonitrile-butadiene rubber with acrylonitrile generated in the Step3 through the catalyst 4;
step 5: under the condition 5, the nitrile rubber is dissolved in an organic solvent and then hydrogenated nitrile rubber is produced by the catalyst 5.
The catalyst 1 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with 10 times of desalted water, 0.1 time of nitric acid, 4 times of kaolin and 6 times of silica sol by mass; the catalyst 2 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 8 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.2 time of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 6 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 4 times of the mass of the silicon-aluminum-; the catalyst 3 is a mixture of a catalyst which takes coarse-pore silica gel as a carrier and supports vanadium oxide and a catalyst which supports tungsten oxide; the catalyst 4 is a catalyst in which hydrogen peroxide and ferrous chloride coexist; the catalyst 5 is a rhodium-based catalyst.
Setting the condition 1 refers to that the reaction temperature is 470 ℃, and the reaction pressure is 1.1MPa in the circulating fluidized bed; setting the condition 2 refers to that the reaction temperature is 500 ℃ and the reaction pressure is 0.7MPa in the circulating fluidized bed; setting the condition 3 to be 500 ℃ and 0.2 MPa; setting the condition 4 to be 30 ℃ and 1.0 MPa; the set condition 5 means that the reaction temperature is 60 ℃ and the reaction pressure is 5 MPa.
The mass fraction of the methanol for treatment accounts for 99 percent, wherein the content of impurity iron is lower than 80 ppm.
Conditions 1 and 2 were set using high purity nitrogen as a carrier gas.
The butene is a mixture of n-butene, isobutene, cis-2-butene and trans-2-butene, wherein the mass fraction of the isobutene in the mixture is 10%.
In the set condition 5, the mass of the added catalyst 5 is 1% of that of the nitrile rubber, and the organic solvent for dissolving the nitrile rubber is chlorobenzene.
The setting condition 4 further includes a polymerization degree increasing regulator alkyl mercaptan, an emulsifier, an electrolyte and a polymerization terminator.
The emulsifier is fatty acid soap, the electrolyte is sodium sulfate, and the polymerization terminator is hydroquinone.
Example 3
A method for deep processing of process gas for preparing olefin from methanol comprises the following steps:
step1, under the condition of setting the condition 1, separating ethylene, propylene I, butylene, butadiene and other impurity gases from the process gas prepared by the methanol through the catalyst 1 through a separating device, wherein the mass fraction of the process gas is as follows: 42% of ethylene, 40% of propylene I, 10% of butylene, 2% of butadiene and 6% of other impurity gases; other contaminant gases include from methane, ethane to carbon ten, and so forth.
Step 2: under the condition 2, ethylene and butylene react through a catalyst 2 to generate propylene II which is 50 percent of the mass of the ethylene;
step 3: propylene I separated in Step1 and propylene II prepared in Step2 are added and mixed to form propylene, and under the condition of setting the condition 3, the propylene reacts with ammonia gas with the molar ratio of 1.2 times that of the propylene, air with the molar ratio of 2.5 times that of the propylene and water vapor with the molar ratio of 3 times that of the propylene through a catalyst 3 to form acrylonitrile with the mass percent of 72 percent of that of the propylene;
step 4: under the condition of setting the condition 4, the butadiene separated in the Step1 and 6 times of the butadiene are added to generate acrylonitrile-butadiene rubber with acrylonitrile generated in the Step3 through the catalyst 4;
step 5: under the condition 5, the nitrile rubber is dissolved in an organic solvent and then hydrogenated nitrile rubber is produced by the catalyst 5.
The catalyst 1 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 5 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.06 times of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 3 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 4 times of the mass of the silicon-aluminum-phosphorus; the catalyst 2 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 6 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.12 time of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 4 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 3 times of the mass of the silicon-aluminum-; the catalyst 3 is a mixture of a catalyst in which iron oxide is supported on a coarse-pore silica gel as a carrier, a catalyst in which cobalt oxide is supported, and a catalyst in which nickel oxide is supported; the catalyst 4 is a catalyst in which hydrogen peroxide and ferrous sulfate coexist; the catalyst 5 is a palladium catalyst.
Setting the condition 1 refers to that the reaction temperature is 420 ℃, and the reaction pressure is 0.5MPa in the circulating fluidized bed; setting the condition 2 refers to that the reaction temperature is 470 ℃, and the reaction pressure is 0.4MPa in the circulating fluidized bed; setting the condition 3 to be that the reaction temperature is 430 ℃ and the reaction pressure is 0.2 MPa; setting the condition 4 to be 20 ℃ and 1.0 MPa; the set condition 5 means that the reaction temperature was 40 ℃ and the reaction pressure was 3 MPa.
The mass fraction of the methanol for treatment accounts for 95 percent, wherein the content of impurity iron is lower than 80 ppm.
Conditions 1 and 2 were set using high purity nitrogen as a carrier gas.
The butene is a mixture of n-butene, isobutene, cis-2-butene and trans-2-butene, wherein the mass fraction of the isobutene in the mixture is 8%.
In the set condition 5, the mass of the added catalyst 5 is 0.7% of that of the nitrile rubber, and the organic solvent for dissolving the nitrile rubber is pyridine.
The setting condition 4 further includes a polymerization degree increasing regulator alkyl mercaptan, an emulsifier, an electrolyte and a polymerization terminator.
The emulsifier is abietic acid soap, the electrolyte is sodium sulfate, and the polymerization terminator is hydroquinone.
Example 4
A method for deep processing of process gas for preparing olefin from methanol comprises the following steps:
step1, under the condition of setting the condition 1, separating ethylene, propylene I, butylene, butadiene and other impurity gases from the process gas prepared by the methanol through the catalyst 1 through a separating device, wherein the mass fraction of the process gas is as follows: 36% of ethylene, 39% of propylene I, 15% of butylene, 5% of butadiene and 5% of other impurity gases; other contaminant gases include from methane, ethane to carbon ten, and so forth.
Step 2: under the condition 2, ethylene and butylene react through the catalyst 2 to generate propylene II which is equivalent to 45 percent of the mass of the ethylene;
step 3: propylene I separated in Step1 and propylene II prepared in Step2 are added and mixed to form propylene, and under the condition of setting the condition 3, the propylene reacts with ammonia gas with the molar ratio of 1.1 times that of the propylene, air with the molar ratio of 2.0 times that of the propylene and water vapor with the molar ratio of 3.2 times that of the propylene through a catalyst 3 to generate 69 percent of acrylonitrile corresponding to the mass of the propylene;
step 4: under the condition of setting the condition 4, butadiene separated in Step1 and 7 times of butadiene are added to generate acrylonitrile-butadiene rubber with acrylonitrile generated in Step3 through a catalyst 4;
step 5: under the condition 5, the nitrile rubber is dissolved in an organic solvent and then hydrogenated nitrile rubber is produced by the catalyst 5.
The catalyst 1 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 6 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.07 time of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 3 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 6 times of the mass of the silicon-aluminum-phosphorus; the catalyst 2 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 5 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.09 times of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 3 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 4 times of the mass of the silicon-aluminum-; the catalyst 3 is a mixture of a catalyst in which bismuth oxide is supported on a coarse-pore silica gel as a carrier, a catalyst in which vanadium oxide is supported, and a catalyst in which tungsten oxide is supported; the catalyst 4 is a catalyst in which hydrogen peroxide and ferrous chloride coexist; the catalyst 5 is a rhodium-based catalyst.
Setting the condition 1 refers to that the reaction temperature is 470 ℃, and the reaction pressure is 1.1MPa in the circulating fluidized bed; setting the condition 2 refers to that the reaction temperature is 480 ℃ and the reaction pressure is 0.4MPa in the circulating fluidized bed; setting the condition 3 to be that the reaction temperature is 470 ℃ and the reaction pressure is 0.2 MPa; setting the condition 4 to be that the reaction temperature is 15 ℃ and the reaction pressure is 1.0 MPa; the set condition 5 means that the reaction temperature is 60 ℃ and the reaction pressure is 2 MPa.
The mass fraction of the methanol for treatment accounts for 97 percent, wherein the content of impurity iron is lower than 80 ppm.
Conditions 1 and 2 were set using high purity nitrogen as a carrier gas.
The butene is a mixture of n-butene, isobutene, cis-2-butene and trans-2-butene, wherein the mass fraction of the isobutene in the mixture is 8%.
In the set condition 5, the mass of the added catalyst 5 is 0.9% of that of the nitrile rubber, and the organic solvent for dissolving the nitrile rubber is acetone.
The setting condition 4 further includes a polymerization degree increasing regulator alkyl mercaptan, an emulsifier, an electrolyte and a polymerization terminator. The emulsifier is fatty acid soap, the electrolyte is sodium phosphate, and the polymerization terminator is hydroquinone.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (8)
1. A method for deep processing of process gas for preparing olefin from methanol is characterized by comprising the following steps: the method comprises the following steps:
step1, under the condition of setting the condition 1, separating ethylene, propylene I, butylene, butadiene and other impurity gases from the process gas prepared by the methanol through the catalyst 1 through a separating device, wherein the mass fraction of the process gas is as follows: 30-43% of ethylene, 35-44% of propylene I, 10-15% of butylene, 2-8% of butadiene and 5-7% of other impurity gases;
step 2: under the condition of setting the condition 2, ethylene and butylene react through a catalyst 2 to generate propylene II which is 30-60% of the mass of the ethylene;
step 3: propylene I separated from Step1 and propylene II prepared from Step2 are added and mixed to form propylene, and under the condition of setting the condition 3, the propylene reacts with ammonia gas with the molar ratio of 1.1-1.2 times that of the propylene, air with the molar ratio of 2.0-3.0 times that of the propylene and water vapor with the molar ratio of 2.7-3.2 times that of the propylene through a catalyst 3 to generate 65-77% of acrylonitrile corresponding to the mass of the propylene;
step 4: under the condition of setting the condition 4, butadiene separated in Step1 and additionally 4-8 molar multiples of butadiene are added to generate acrylonitrile-butadiene rubber with acrylonitrile generated in Step3 through a catalyst 4;
step 5: under the condition of setting the condition 5, dissolving the nitrile rubber in an organic solvent, and generating hydrogenated nitrile rubber by a catalyst 5;
wherein, the set condition 1 refers to that the reaction temperature is 400-470 ℃, and the reaction pressure is 0-1.1MPa in the circulating fluidized bed; setting the condition 2 to be a circulating fluidized bed with the reaction temperature of 420-500 ℃ and the reaction pressure of 0-0.7 MPa; the set condition 3 is that the reaction temperature is 400-; setting the condition 4 to be 5-30 ℃ and 0-1.0 MPa; the set condition 5 means that the reaction temperature is 20-60 ℃ and the reaction pressure is 0.5-5 MPa.
2. The method for further processing the process gas for preparing the olefin from the methanol according to claim 1, which is characterized in that: the catalyst 1 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 2-10 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.01-0.1 time of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 1-4 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 2-6 times of the mass of the silicon-aluminum-phosphorus; the catalyst 2 is prepared by mixing a silicon-aluminum-phosphorus molecular sieve with desalted water which is 1-8 times of the mass of the silicon-aluminum-phosphorus molecular sieve, nitric acid which is 0.05-0.2 time of the mass of the silicon-aluminum-phosphorus molecular sieve, kaolin which is 2-6 times of the mass of the silicon-aluminum-phosphorus molecular sieve and silica sol which is 1-4 times of the mass of the silicon-aluminum-; the catalyst 3 is one or a mixture of two or more of catalysts which take coarse-pore silica gel as a carrier and load oxides of heavy metals of antimony, bismuth, tungsten, iron, cobalt and nickel; the catalyst 4 refers to a catalyst in which hydrogen peroxide and ferrous salt coexist; the catalyst 5 is a palladium or rhodium catalyst.
3. The method for further processing the process gas for preparing the olefin from the methanol as claimed in claim 1, wherein the mass fraction of the methanol for treatment is 90-99%, and the content of the impurity iron is lower than 80 ppm.
4. The method for the process gas deep processing of the methanol to olefin as claimed in claim 1, wherein the conditions 1 and 2 are set to high purity nitrogen as the carrier gas.
5. The method of claim 1, wherein the butene is a mixture of n-butene, isobutene, cis-2-butene, and trans-2-butene, and the mass fraction of isobutene in the mixture is 5-10%.
6. The method for processing the methanol to olefin further according to claim 1, wherein the mass of the catalyst 5 added under the set condition 5 is 0.5-1% of that of the nitrile rubber, and the organic solvent for dissolving the nitrile rubber is one or two of benzene, chlorobenzene, pyridine and acetone.
7. The method of claim 1, wherein the set condition 4 further comprises alkyl mercaptan as a polymerization degree regulator, an emulsifier, an electrolyte and a polymerization terminator.
8. The method of claim 7, wherein the emulsifier is rosin acid soap or fatty acid soap, the electrolyte is potassium chloride, sodium phosphate or sodium sulfate, and the polymerization terminator is hydroquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810350615.5A CN108530580B (en) | 2018-04-18 | 2018-04-18 | Process gas deep processing method for preparing olefin from methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810350615.5A CN108530580B (en) | 2018-04-18 | 2018-04-18 | Process gas deep processing method for preparing olefin from methanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108530580A CN108530580A (en) | 2018-09-14 |
| CN108530580B true CN108530580B (en) | 2020-09-08 |
Family
ID=63478377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810350615.5A Active CN108530580B (en) | 2018-04-18 | 2018-04-18 | Process gas deep processing method for preparing olefin from methanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108530580B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335623A (en) * | 2011-07-08 | 2012-02-01 | 中国天辰工程有限公司 | Fluidized bed catalyst and preparation method thereof |
| CN103691491A (en) * | 2013-12-31 | 2014-04-02 | 中国天辰工程有限公司 | Method for removing sodium by silicon-aluminum-phosphor molecular sieve catalyst |
-
2018
- 2018-04-18 CN CN201810350615.5A patent/CN108530580B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335623A (en) * | 2011-07-08 | 2012-02-01 | 中国天辰工程有限公司 | Fluidized bed catalyst and preparation method thereof |
| CN103691491A (en) * | 2013-12-31 | 2014-04-02 | 中国天辰工程有限公司 | Method for removing sodium by silicon-aluminum-phosphor molecular sieve catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108530580A (en) | 2018-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103301876B (en) | A kind of preparation method of straight-chain olefin skeleton isomerization catalyst | |
| CN108607550A (en) | A kind of gold catalysts producing methyl methacrylate and its application | |
| CN101204664A (en) | Multiphase catalytic oxidation cyclohexane catalyst for cyclohexanone and cyclohexanol and preparation method thereof | |
| CN107971026A (en) | Combination catalyst for producing light olefins | |
| CN105254462A (en) | Process for producing olefin from methanol and for co-producing gasoline and aromatic hydrocarbon | |
| CN105152842B (en) | A kind of acetylene hydrogenation prepares the reaction system and method for ethene | |
| CN108530580B (en) | Process gas deep processing method for preparing olefin from methanol | |
| CN110385141B (en) | Composite catalyst for directly preparing aromatic hydrocarbon from synthesis gas and preparation method thereof | |
| CN102872901B (en) | Preparation method of low-carbon hydrocarbon aromatization catalyst | |
| CN108212204B (en) | Catalyst for directly preparing high-carbon olefin from methane by microwave assistance and catalysis process | |
| CN110327969A (en) | A kind of CO2Add catalyst of hydrogen producing light olefins and preparation method thereof, application | |
| CN102211036B (en) | A kind of modified molecular sieve catalyst and its precursor and preparation method thereof | |
| CN103304360B (en) | Butadiene product and preparation method thereof | |
| CN105980340A (en) | Integration of MTO with on purpose butadiene | |
| CN103301838A (en) | Catalyst and application as well as preparation method thereof | |
| CN107056670A (en) | A kind of preparation method of two tertiary base peroxide | |
| US9701910B2 (en) | Process for the production of olefins through FT based synthesis | |
| CN107952469B (en) | Bifunctional catalyst and preparation method and application thereof | |
| CN107118093B (en) | Method for producing acrylic acid | |
| CN104692994B (en) | Method by micro passage reaction synthesis ethylidene norbornene | |
| CN109608301B (en) | Method for preparing butylene and butadiene through catalytic dehydrogenation of butane | |
| CN104098531B (en) | A kind of synthetic method of 1,2-epoxy butane | |
| EP3303269B1 (en) | Process for the selective hydrogenation of acetylene to ethylene | |
| CN107267200B (en) | A method of it is alkylated by alkane and alkene | |
| CN110041154A (en) | A method of it catalyzing and synthesizing gas conversion and prepares low-carbon alkene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |