CN112745184B - Method for producing isooctene by overlapping mixed C4 raw material with high olefin content - Google Patents
Method for producing isooctene by overlapping mixed C4 raw material with high olefin content Download PDFInfo
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- CN112745184B CN112745184B CN201911049326.2A CN201911049326A CN112745184B CN 112745184 B CN112745184 B CN 112745184B CN 201911049326 A CN201911049326 A CN 201911049326A CN 112745184 B CN112745184 B CN 112745184B
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- 239000002994 raw material Substances 0.000 title claims abstract description 60
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 title abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 190
- 239000003112 inhibitor Substances 0.000 claims abstract description 78
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims description 129
- 229920005989 resin Polymers 0.000 claims description 129
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 58
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 52
- 229910052736 halogen Inorganic materials 0.000 claims description 48
- 150000002367 halogens Chemical class 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 45
- 238000011144 upstream manufacturing Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003456 ion exchange resin Substances 0.000 claims description 23
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 23
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005342 ion exchange Methods 0.000 claims description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims 8
- 239000001282 iso-butane Substances 0.000 claims 4
- 235000013847 iso-butane Nutrition 0.000 claims 4
- 239000001294 propane Substances 0.000 claims 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims 4
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims 3
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 10
- 150000003460 sulfonic acids Chemical class 0.000 description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006471 dimerization reaction Methods 0.000 description 6
- 238000005829 trimerization reaction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005658 halogenation reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- -1 carbon carbonium ions Chemical group 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
- C07C2531/10—Ion-exchange resins sulfonated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for producing isooctene by the superposition of a mixed C4 raw material with high olefin content. Aiming at the mixed C-IV raw material with high olefin content, the invention takes the raw material composition and the reaction characteristics into comprehensive consideration and finely divides the reaction area; grading filling is carried out on the catalyst aiming at different reaction areas, and different operation conditions are adopted. Under the conditions of high selectivity and conversion rate, no over-temperature of the device and less byproducts, the dosage of the inhibitor is greatly reduced, and the economic benefit of the device is improved.
Description
Technical Field
The invention relates to a method for producing isooctene by the superposition of a mixed C4 raw material with high olefin content.
Background
With the continuous improvement of the living standard of people, the country pays more and more attention to environmental protection, and the countries in 2017 issue documents, so that the MTBE cannot be added into the gasoline while the ethanol gasoline is greatly popularized in the country. However, the number of the domestic MTBE devices is large, and how to reasonably reform the MTBE devices enables the reformed MTBE devices to retain the function of separating carbon four and carbon four, and convert mixed carbon four into products with economic benefits, so that the MTBE devices are an urgent research task.
For the MTBE plant, the normal feed is a C4 blend feed with an olefin content of 15 wt% to 22 wt%. However, since there are many MTBE units and there are great differences in the feedstocks of each refinery or chemical plant, the isobutene concentration in some feedstocks exceeds the standard by 22 wt% to 30 wt%. When the raw materials are superposed, a large amount of inhibitor is required to be added to reduce the generation of trimerization and tetramerization products, and the economic benefit of the device is reduced linearly due to the high cost of the inhibitor and the large amount of the inhibitor, and the operation difficulty is improved. If no inhibitor is added, not only can the by-products be greatly increased, but also the bed layer is easy to generate temperature runaway phenomenon. Therefore, it is a necessary task to ensure that the amount of inhibitor used and thus the cost can be reduced by using a method which can ensure that the polymerization reaction is carried out by using the mixed C4 with high olefin content under the conditions of higher conversion rate and selectivity and under the conditions of no temperature runaway and no increase of byproducts.
Disclosure of Invention
The invention aims to provide a method for producing isooctenes by the superposition of mixed C4 with high olefin content. The method can greatly reduce the addition of the inhibitor, further greatly reduce the cost, simultaneously obtain higher conversion rate and selectivity, and solve the problems of easy temperature runaway and more byproducts of the device.
According to the characteristic of the mixed C4 polymerization reaction with high olefin content, the invention finely divides three reaction sections: a reaction zone without inhibitor, a reaction zone in which the inhibitor is flexibly added, and a reaction zone in which the inhibitor must be contained. Catalysts with different performances are graded and filled in the unused areas, and the reaction conditions of the areas are coupled and matched according to the catalysts and the reaction characteristics, so that the aim of the invention can be achieved.
The invention discloses a method for producing isooctene by mixing C4 superposition, which comprises the following steps:
the mixed C4 raw material containing isobutene passes through a superposition reaction zone under superposition process conditions, and the superposition reaction zone comprises an upstream reaction section, a middle downstream reaction section and a downstream reaction section along the feeding direction; wherein the upstream reaction section is filled with a common laminated resin A with strong acidity and large acid distribution, and no inhibitor is added; filling resin B with strong acidity and large acid distribution in the middle and upstream reaction section, and selectively adding an inhibitor in the reaction section; filling halogenated resin C with strong acidity and large acid distribution in the middle and downstream reaction sections, and selectively adding an inhibitor in the reaction sections; filling halogenated resin D with moderate acidity and large acid distribution in a downstream reaction section, and selectively adding an inhibitor in the reaction section; wherein, the inhibitor is added to at least one section of the middle upstream reaction section, the middle downstream reaction section and the downstream reaction section.
In the invention, along the feeding direction, the whole superposition reaction zone is divided into four different reaction sections, namely an upstream reaction section, a middle downstream reaction section and a downstream reaction section. The different reaction stages can be arranged in one reactor or in different reactors.
Further, "optionally adding an inhibitor" means that the inhibitor may or may not be added.
Further, the resin A, the resin B and the resin C are sulfonic acid type ion exchange resins, and halogenated sulfonic acid type ion exchange resins can be selectively adopted. Wherein the ion exchange equivalent of the resin A is 2.0-6.0 mg/g, and the halogen acid ratio is 0. The ion exchange equivalent of the resin B is equivalent to that of the resin A, and the halogen acid ratio is 0-50%, preferably 20-50%. The ion exchange equivalent of the resin C is equivalent to that of the resin A, and the halogen acid ratio is 50-90%. The resin D is phosphoric acid type ion exchange resin, the ion exchange equivalent is 3.0-7.0 mg/g, and the halogen acid ratio is 50-90%. Wherein the halogen acid ratio is defined as: the molar ratio of halogen element to sulfonate (or phosphate) in the resin catalyst. The halogen element can be selected from one of chlorine and bromine, and is preferably bromine. The optional use of a halogenated sulfonic acid type ion exchange resin means that a halogenated sulfonic acid type ion exchange resin is selected as necessary, and a non-halogenated sulfonic acid type ion exchange resin may be selected.
Further, the inhibitor added in the present invention is an oxygen-containing compound, generally an alcohol, preferably t-butanol. The total addition of the inhibitor is 0.5-2.0% of the total feed mass. The added inhibitor can be diluted by water, and the water content of the inhibitor is the percentage of the water to the total mass of the inhibitor after the water is added.
The amount of the inhibitor added into the middle upstream reaction section can be 0-100% of the total mass of the inhibitor, the water content of the inhibitor is generally 0-50%, and the preferable amount is 0-30%; the halogen acid ratio of the resin B is generally 0-50%, preferably 20-50%; and the amount of inhibitor used and the amount of halogenation of resin B cannot be both 0. Whether or not inhibitors are added in this stage and halogenated resins are used depends on the isobutene content of the C4 feedstock. When the mass content of isobutene in the raw materials is 22-25%, no inhibitor can be added, and the halogen acid ratio of the corresponding resin B can be 50-90%; when the mass content of isobutene in the raw materials is 25-30%, an inhibitor needs to be added in the section, the dosage of the inhibitor is 25-100% of the total mass (including water content) of the inhibitor, and the halogenation amount of the resin B can be 0-50%.
In the middle and downstream reaction sections, the amount of the added pure inhibitor is 0-100%, preferably 25-100% of the total inhibitor (including water content). The water content of the inhibitor added in the section is generally 0-80%, and preferably 20-50%.
The pure inhibitor added in the downstream reaction section accounts for 0-100%, preferably 25-100% of the total inhibitor (including water content). The water content of the inhibitor added in the section is generally 0-80%, and preferably 20-50%.
In the polymerization reaction zone of the present invention, the volume fraction of resin charged in each reaction zone is generally: 5% -25% of resin A, preferably 8% -15%; 5% -25% of resin B, preferably 8% -15%, and 10% -40% of resin C, preferably 15% -25%; 25-80% of resin D, preferably 40-70%.
In the C4 raw material containing isobutene, the content of isobutene is 22-30%.
The process conditions of the superposition reaction are as follows: the average reaction temperature is 40-65 ℃, the inlet temperature of each reaction section is generally 10-45 ℃, the single-section temperature rise of each reaction section is generally controlled to be 12-25 ℃, and the total liquid hourly space velocity of the mixed C4 raw material is 0.8 h -1 ~1.4 h -1 Preferably 1.0 h -1 ~1.2 h -1 。
Compared with the prior art, the invention has the beneficial effects that:
1. when the raw material is mixed carbon-four-C4 with high olefin content, the raw material and the reaction characteristics are comprehensively considered, the reaction areas are finely divided, the catalysts are filled in different reaction areas in a classified grading manner, and different operation conditions are adopted. Under the conditions of high selectivity and conversion rate of the reaction, no over-temperature of the device and less byproducts, the dosage of the inhibitor is greatly reduced, and the economic benefit of the device is greatly improved.
2. The halogenated resin is obtained by halogenating sulfonic acid or phosphoric acid type ion exchange resin with halogen. During halogenation, the introduced halogen groups are grafted into the ends of the molecular structure (position) of the resin. The halogen group is a polar group, has electronegativity and larger volume, so the introduced halogen group forms a steric hindrance effect on a resin structure. The presence of this steric hindrance effect, which has a repulsive effect, results in a reduced chance of the dimerization product of isobutylene contacting the resin acidity and reduces the possibility of further polymerization into trimerization and tetramerization products. Therefore, the halogenated resin catalyst used in the invention can inhibit the generation of polymeric products such as trimerization, tetramerization and the like in the polymerization process under the premise of reducing the dosage of the inhibitor.
3. In the method of the invention, in the upstream reaction stage of the reaction, because a large amount of tertiary carbon carbonium ions need to be generated on the resin catalyst with stronger acidity in the initial stage of the dimerization reaction of isobutene, no inhibitor needs to be added at the moment, and the matched catalyst is the sulfonic acid resin with stronger acidity. In the mid-upstream reaction zone of the reaction, since a small amount of isobutylene dimerization product is already present, it is necessary to suppress the continued reaction of the dimerization product into trimer and tetramer, and therefore it is necessary to minimize the amount of dimer activated by the catalyst. At the moment, if the mass content of isobutene in the raw materials is 22-25%, the inhibitor can not be added, but halogenated sulfonic acid resin is needed to inhibit the generation of trimerization and tetramer; if the mass content of isobutene in the raw material is 25-30%, the halogenated sulfonic acid resin can not completely inhibit the generation of trimerization and tetramer, so that the non-halogenated sulfonic acid resin can be adopted, and a certain amount of inhibitor is added. In the middle and downstream reaction stages of the reaction, a large amount of dimerization product is already present at this stage, so that the generation of trimerization and tetramerization is controlled by using halogenated sulfonic acid resin and adding a certain amount of inhibitor. In the downstream reaction stage of the reaction, only a small amount of isobutylene remains unreacted in this stage, and therefore a phosphoric acid resin having a weaker acidity than a sulfonic acid resin is used. Since a large amount of dimerization product is present at this stage, the phosphoric acid resin needs to be halogenated and a certain amount of inhibitor needs to be present.
4. In the present invention, the inhibitor used is preferably an inhibitor diluted with water. The inhibitor is dissolved in water, and the inhibitor after being partially ionized by water is easier to form active matters on the surface of the catalyst, so that the speed of occupying tertiary carbon carbonium ions is higher, the utilization efficiency of the inhibitor can be improved, and the dosage of the pure inhibitor can be reduced. In addition, the addition of trace water does not affect the post-treatment of the dimer, isooctene.
Detailed Description
In the present invention, the preparation of the polymerization catalyst, i.e., the sulfonic acid resin and the phosphoric acid resin, is conventional in the art and will not be described in detail. The resin is halogenated to obtain halogenated resin, and the halogenated resin is prepared through halogenation reaction on cation exchange resin and subsequent preparation of sulfonic acid resin and phosphoric acid resin. Resin A is a conventional sulfonic acid resin, resin B can be a conventional sulfonic acid resin or a halogenated sulfonic acid resin, resin C is a halogenated sulfonic acid resin with high halogen acid ratio, and resin D is a halogenated phosphoric acid resin with high halogen acid ratio.
TABLE 1 catalyst physicochemical Properties index
Raw materials: two mixed C4 raw materials with different isobutene contents are selected, wherein the isobutene content in the raw material 1 is 24% by mass, the isobutene content in the raw material 2 is 29% by mass, and the composition of the raw materials is shown in Table 2. The raw materials and the products are subjected to composition analysis by gas chromatography.
TABLE 2C 4 blend stock
Calculation of conversion and selectivity: the isobutene conversion is the molar percentage of the amount of isobutene converted to the amount of isobutene in the feed. Isooctene selectivity is the molar percentage of the amount of isobutylene forming isooctenes relative to the amount of isobutylene participating in the reaction.
Comparative example 1
The reaction part was not segmented. The raw material 1 is adopted as a reaction raw material, resin A (exchange equivalent is 5.2 mg/g) is adopted as a catalyst, tert-butyl alcohol is adopted as an inhibitor, the addition amount is 1.2 wt% of the raw material, and the inhibitor is added from a reaction inlet. At the average reaction temperature of 63 ℃ and the total volume space velocity of 1.0h -1 Under the conditions of (1), the conversion of isobutylene was 91.1% and the selectivity for isooctene was 90.2%.
Comparative example 2
The raw material 2 is adopted as a reaction raw material, resin A (exchange equivalent is 5.4 mg/g) is adopted as a catalyst, tert-butyl alcohol is also adopted as an inhibitor, the adding amount is 1.5 wt% of the raw material, and the inhibitor is added from a reaction inlet. At the average reaction temperature of 70 ℃ and the total volume space velocity of 1.0h -1 Under the conditions of (1), the conversion of isobutylene was 90.3%, and the selectivity to isooctene was 91.3%.
Example 1
The filling mode of the catalyst is as follows: resin A (exchange equivalent is 5.2 mg/g, halogen acid ratio is 0) is filled in the upstream reaction section of the reaction, and the volume fraction of the resin A is 10 percent; filling resin B (exchange equivalent is 5.2 mg/g, halogen acid ratio is 50) in the middle and upstream reaction section, wherein the volume fraction of the resin B is 10%; filling resin C (exchange equivalent is 5.2 mg/g, halogen acid ratio is 80) in the middle and downstream reaction sections, wherein the volume fraction of the resin C is 20%; the downstream reaction zone was charged with resin D (exchange equivalent of 6.1 mg/g, halogen acid ratio of 80) in a volume fraction of 60%.
The raw material 1 is adopted as a reaction raw material, tertiary butanol is added as an inhibitor in the middle and downstream reaction sections, and the adding amount is 1.0 wt% of the raw material amount. The average reaction temperature of the upstream reaction section is 39 ℃, and the volume space velocity is 12 h -1 The average reaction temperature of the middle and upstream reaction sections is 55 ℃, and the space velocity is 12 h -1 The average reaction temperature of the middle and downstream reaction sections is 72 ℃ and the volume space velocity is 6 h -1 The average reaction temperature of the downstream reaction section is 88 ℃, and the volume space velocity is 2 h -1 Under the conditions ofThe isobutene conversion was 92.1% and the isooctene selectivity was 90.8%.
Example 2
The catalyst loading was the same as in example 1.
The raw material 1 is adopted as a reaction raw material, tertiary butanol with water content of 50 percent is added as an inhibitor in the middle and lower sections, and the pure tertiary butanol accounts for 0.8 percent of the raw material by weight. The average reaction temperature of the upstream reaction section is 39 ℃, and the volume space velocity is 12 h -1 The average reaction temperature of the middle and upstream reaction sections is 55 ℃, and the volume space velocity is 12 h -1 The average reaction temperature of the middle and downstream reaction sections is 72 ℃, and the volume space velocity is 6 h -1 The average reaction temperature of the downstream reaction section is 88 ℃ and the volume space velocity is 2 h -1 Under the conditions of (1), the conversion of isobutylene was 91.3%, and the selectivity for isooctene was 92.3%.
Example 3
The filling mode of the catalyst is as follows: resin A (exchange equivalent of 5.4 mg/g, halogen acid ratio of 0) was packed in the upstream reaction section, and the volume fraction of resin A was 8%; filling resin B (exchange equivalent is 5.4 mg/g, halogen acid ratio is 0) in the middle-upstream reaction section, wherein the volume fraction of the resin B is 8%; filling resin C (exchange equivalent is 5.4 mg/g, halogen acid ratio is 80) in the middle and downstream reaction sections, wherein the volume fraction of the resin C is 17%; the downstream reaction zone was charged with resin D (exchange equivalent of 6.2 mg/g, halogen acid ratio of 80) in a volume fraction of 67% based on resin C.
The raw material 2 is adopted as a reaction raw material, tertiary butanol with water content of 50 percent is added as an inhibitor in a middle-upstream reaction section, and the pure tertiary butanol accounts for 0.5 percent by weight of the raw material. Adding tertiary butanol containing 50% of water as an inhibitor into a downstream reaction section, wherein the pure tertiary butanol accounts for 0.5 wt% of the raw material. The average reaction temperature of the upstream reaction section is 45 ℃, and the volume space velocity is 14 h -1 The average reaction temperature of the middle and upstream reaction sections is 65 ℃, and the volume space velocity is 13 h -1 The average reaction temperature of the middle and downstream reaction sections is 85 ℃ and the volume space velocity is 7 h -1 The average reaction temperature of the downstream reaction section is 105 ℃, and the volume space velocity is 1.5 h -1 Under the conditions of (1), the conversion of isobutylene was 92.8% and the selectivity to isooctene was 91.6%.
Example 4
The filling mode of the catalyst is as follows: resin A (exchange equivalent of 5.4 mg/g, halogen acid ratio of 0) was packed in the upstream reaction section, and the volume fraction of resin A was 10%; filling a resin B (exchange equivalent is 5.4 mg/g, halogen acid ratio is 0) in the middle-upstream reaction section, wherein the volume fraction of the resin B is 10%; filling resin C (exchange equivalent is 5.4 mg/g, halogen acid ratio is 80) in the middle and downstream reaction sections, wherein the volume fraction of the resin C is 20%; the downstream reaction zone was charged with resin D (exchange equivalent of 6.2 mg/g, halogen acid ratio of 80) in a volume fraction of 60%.
The raw material 2 is adopted as a reaction raw material, tertiary butanol with water content of 50 percent is added as an inhibitor in a middle-upstream reaction section, and the pure tertiary butanol accounts for 0.5 percent by weight of the raw material. The tertiary butanol with water of 50 percent is added into the middle and downstream reaction sections to be used as an inhibitor, and the pure tertiary butanol accounts for 0.5 percent of the weight of the raw material. The average reaction temperature of the upstream reaction section is 46 ℃, and the volume space velocity is 12 h -1 The average reaction temperature of the middle and upstream reaction sections is 66 ℃ and the volume space velocity is 12 h -1 The average reaction temperature of the middle and downstream reaction sections is 84 ℃ and the volume space velocity is 6 h -1 The average reaction temperature of the downstream reaction section is 103 ℃, and the volume space velocity is 2 h -1 Under the conditions of (1), the conversion of isobutylene was 92.4% and the selectivity for isooctene was 91.3%.
In each example, the pure inhibitor used in comparative example 1, example 1 and example 2 using the raw material 1 in percentage of the raw material amount is: 1.2 wt%, 1.0 wt%, 0.8 wt%; the pure inhibitors of comparative example 2, example 3 and example 4 using feed 2 were used in the following amounts in percent of the feed, respectively: 1.5 wt%, 1.0 wt%, 1.0 wt%. From the results, it can be seen that, in the case of using the same raw material, the use amount of the inhibitor can be reduced by the stage-graded filling method of the present invention, and on this basis, if the aqueous inhibitor is used, the effect is better, and the use amount of the inhibitor can be further reduced, so that the efficient use of the inhibitor is achieved.
Therefore, when the content of olefin (22 wt% -30 wt%) in the mixed C4 raw material is higher, the method provided by the invention can reduce the dosage of the inhibitor and improve the economy of the device on the premise of achieving the isobutene conversion rate and selectivity which are not lower than those of the conventional method.
Claims (4)
1. A method for producing isooctenes by mixing C4 raw material superposition, which comprises the following contents:
passing a mixed C4 feedstock containing isobutylene under polymerization process conditions through a polymerization reaction zone; along the feeding direction, the superposition reaction zone comprises an upstream reaction section, a middle downstream reaction section and a downstream reaction section;
wherein, the upstream reaction section is filled with resin A: the resin A is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.2 mg/g, and the halogen acid ratio is 0; the volume fraction of the resin A is 10 percent;
filling resin B in the middle and upstream reaction section: the resin B is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.2 mg/g, and the halogen acid ratio is 50 percent; the volume fraction of the resin B is 10 percent;
filling halogenated resin C in the middle and downstream reaction sections, and adding inhibitor tert-butyl alcohol, wherein the addition amount is 1.0 wt% of the raw material amount; the resin C is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.2 mg/g, and the halogen acid ratio is 80 percent; the volume fraction of the resin C is 20 percent;
The downstream reaction section is filled with halogenated resin D: the resin D is phosphoric acid type ion exchange resin, the ion exchange equivalent is 6.1mg/g, and the halogen acid ratio is 80 percent; the volume fraction of the resin D is 60 percent;
the halogen acid ratio refers to the molar ratio of halogen elements to sulfonate or phosphate radicals in the resin catalyst;
the average reaction temperature of the upstream reaction section is 39 ℃, and the volume space velocity is 12h -1 (ii) a The average reaction temperature of the middle and upstream reaction sections is 55 ℃, and the volume space velocity is 12h -1 (ii) a The average reaction temperature of the middle and downstream reaction sections is 72 ℃, and the volume space velocity is 6h -1 (ii) a The average reaction temperature of the downstream reaction section is 88 ℃, and the volume space velocity is 2h -1 ；
The mixed C-C raw material comprises, by weight, 2.0% of propane, 0.6% of propylene, 42.5% of normal and iso-butane, 24.1% of isobutene, 10.1% of 1-butene, 20.1% of cis and trans 2-butene, 0.5% of C-V and 0.1% of butadiene.
2. A method for producing isooctenes by mixing C4 raw materials and carrying out superposition comprises the following steps:
passing a mixed C4 feedstock containing isobutylene under polymerization process conditions through a polymerization reaction zone; along the feeding direction, the superposition reaction zone comprises an upstream reaction section, a middle downstream reaction section and a downstream reaction section; wherein the content of the first and second substances,
upstream reaction section resin a loading: the resin A is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.2 mg/g, and the halogen acid ratio is 0; the volume fraction of the resin A is 10 percent;
Filling resin B in the middle-upstream reaction section: the resin B is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.2 mg/g, and the halogen acid ratio is 50 percent; the volume fraction of the resin B is 10 percent;
filling halogenated resin C in the middle and downstream reaction sections, and adding tert-butyl alcohol containing 50% of water as an inhibitor, wherein the addition amount of the inhibitor is 0.8 wt% of the raw material amount calculated by the tert-butyl alcohol; the resin C is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.2 mg/g, and the halogen acid ratio is 80 percent; the volume fraction of the resin C is 20 percent;
the downstream reaction section is filled with halogenated resin D: the resin D is phosphoric acid type ion exchange resin, the ion exchange equivalent is 6.1mg/g, and the halogen acid ratio is 80 percent; the volume fraction of the resin D is 60 percent;
the halogen acid ratio refers to the molar ratio of halogen elements to sulfonate or phosphate radicals in the resin catalyst;
the average reaction temperature of the upstream reaction section is 39 ℃, and the volume space velocity is 12h -1 (ii) a The average reaction temperature of the middle and upstream reaction sections is 55 ℃, and the volume space velocity is 12h -1 (ii) a The average reaction temperature of the middle and downstream reaction sections is 72 ℃, and the volume space velocity is 6h -1 (ii) a The average reaction temperature of the downstream reaction section is 88 ℃, and the volume space velocity is 2h -1 ；
The mixed C-C raw material comprises, by weight, 2.0% of propane, 0.6% of propylene, 42.5% of normal and iso-butane, 24.1% of isobutene, 10.1% of 1-butene, 20.1% of cis and trans 2-butene, 0.5% of C-V and 0.1% of butadiene.
3. A method for producing isooctenes by mixing C4 raw materials and carrying out superposition comprises the following steps:
passing a mixed C4 feedstock containing isobutylene under polymerization process conditions through a polymerization reaction zone; along the feeding direction, the superposition reaction zone comprises an upstream reaction section, a middle downstream reaction section and a downstream reaction section; wherein, the first and the second end of the pipe are connected with each other,
filling resin A in an upstream reaction section; the resin A is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.4 mg/g, and the halogen acid ratio is 0; the volume fraction of the resin A is 8 percent;
filling resin B in the upstream-middle reaction section, and adding tert-butyl alcohol containing 50% of water as an inhibitor, wherein the addition amount of the inhibitor is 0.5 wt% of the raw material amount based on the tert-butyl alcohol; the resin B is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.4 mg/g, and the halogen acid ratio is 0; the volume fraction of the resin B is 8 percent;
filling halogenated resin C in the middle and downstream reaction sections; the resin C is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.4 mg/g, and the halogen acid ratio is 80 percent; the volume fraction of resin C is 17%;
filling halogenated resin D in the downstream reaction section, and adding tert-butyl alcohol containing 50% of water as an inhibitor, wherein the addition amount of the inhibitor is 0.5 wt% of the raw material amount calculated by the tert-butyl alcohol; the resin D is phosphoric acid type ion exchange resin, the ion exchange equivalent is 6.2mg/g, and the halogen acid ratio is 80 percent; the volume fraction of the resin D is 67%;
The halogen acid ratio refers to the molar ratio of halogen elements to sulfonate or phosphate radicals in the resin catalyst;
the average reaction temperature of the upstream reaction section is 45 ℃, and the volume space velocity is 14h -1 The average reaction temperature of the middle and upstream reaction sections is 65 ℃, and the volume space velocity is 13h -1 (ii) a The average reaction temperature of the middle and downstream reaction sections is 85 ℃, and the volume space velocity is 7h -1 (ii) a The average reaction temperature of the downstream reaction section is 105 ℃, and the volume space velocity is 1.5h -1 ；
The mixed C-C raw material comprises 1.9% of propane, 0.5% of propylene, 36.8% of normal and iso-butane, 29% of isobutene, 11.6% of 1-butene, 19.5% of cis-trans-2-butene, 0.6% of C-V and 0.1% of butadiene by weight.
4. A method for producing isooctenes by mixing C4 raw materials and carrying out superposition comprises the following steps:
passing a mixed C4 feedstock containing isobutylene under polymerization process conditions through a polymerization reaction zone; along the feeding direction, the superposition reaction zone comprises an upstream reaction section, a middle downstream reaction section and a downstream reaction section; wherein, the first and the second end of the pipe are connected with each other,
filling resin A in an upstream reaction section; the resin A is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.4 mg/g, and the halogen acid ratio is 0; the volume fraction of the resin A is 10 percent;
filling resin B in the upstream-middle reaction section, and adding tert-butyl alcohol containing 50% of water as an inhibitor, wherein the addition amount of the inhibitor is 0.5 wt% of the raw material amount based on the tert-butyl alcohol; the resin B is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.4 mg/g, and the halogen acid ratio is 0; the volume fraction of the resin B is 10 percent;
Filling halogenated resin C in the middle and downstream reaction sections, and adding tert-butyl alcohol containing 50% of water as an inhibitor, wherein the addition amount of the inhibitor is 0.5 wt% of the raw material amount calculated by the tert-butyl alcohol; the resin C is sulfonic acid type ion exchange resin, the ion exchange equivalent is 5.4 mg/g, and the halogen acid ratio is 80 percent; the volume fraction of the resin C is 20 percent;
the downstream reaction section is filled with halogenated resin D: the resin D is phosphoric acid type ion exchange resin, the ion exchange equivalent is 6.2mg/g, and the halogen acid ratio is 80%; the volume fraction of the resin D is 60 percent;
the halogen acid ratio refers to the molar ratio of halogen elements to sulfonate or phosphate radicals in the resin catalyst;
the average reaction temperature of the upstream reaction section is 46 ℃, and the volume space velocity is 12h -1 (ii) a The average reaction temperature of the middle and upstream reaction sections is 66 ℃, and the volume space velocity is 12h -1 (ii) a The average reaction temperature of the middle and downstream reaction sections is 84 ℃, and the volume space velocity is 6h -1 (ii) a The average reaction temperature of the downstream reaction section is 103 ℃, and the volume space velocity is 2h -1 ；
The mixed C-IV raw material comprises 1.9% of propane, 0.5% of propylene, 36.8% of normal and iso-butane, 29% of isobutene, 11.6% of 1-butene, 19.5% of cis-butene, trans-2-butene, 0.6% of C-V and 0.1% of butadiene by weight.
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