阅读说明：本技术 一种烷基化催化剂及其制备方法 (Alkylation catalyst and preparation method thereof ) 是由 陈开生 江含治 于 2021-09-01 设计创作，主要内容包括：本发明公开了一种烷基化催化剂及其制备方法,涉及燃油添加剂技术领域,本发明烷基化催化剂,按百分比计,包括改性二氧化硅作骨料85％、路易斯酸10％、质子酸5％和制孔剂1％；路易斯酸具体为三氯化铝(AICI-(3))或三氟化钇(C-(3)H-(2)F-(9)O-(10)S-(3)Yb)或三氟化镝(DyF-(3))或氯化锌(ZnCI-(2)),质子酸包括浓硫酸(H-(2)SO-(4))或磷酸(H-(3)PO-(4)),制孔剂具体为甲醇(CH-(3)OH),制孔剂按改性二氧化硅加路易斯酸加质子酸总量的1％配制。本发明烷基化催化剂具有良好的抗氧化性、抗爆性、节油效果好,减少了汽车尾气中的有害气体排放,对保护环境和节约能源极为有利,具有良好的经济效益和社会效益。(The invention discloses an alkylation catalyst and a preparation method thereof, relating to the technical field of fuel additives, wherein the alkylation catalyst comprises 85% of modified silicon dioxide as aggregate, 10% of Lewis acid, 5% of protonic acid and 1% of pore-forming agent according to percentage; louis bookThe silicic acid is specifically aluminum trichloride (AICI) 3 ) Or yttrium trifluoride (C) 3 H 2 F 9 O 10 S 3 Yb) or dysprosium trifluoride (DyF) 3 ) Or zinc chloride (ZnCI) 2 ) The protonic acid comprises concentrated sulfuric acid (H) 2 SO 4 ) Or phosphoric acid (H) 3 PO 4 ) The pore-forming agent is methanol (CH) 3 OH), the pore-forming agent is prepared according to 1 percent of the total amount of the modified silicon dioxide, the Lewis acid and the protonic acid. The alkylation catalyst has good oxidation resistance, antiknock property and fuel-saving effect, reduces the emission of harmful gases in automobile exhaust, is extremely favorable for protecting environment and saving energy, and has good economic benefit and social benefit.)

1. The alkylation catalyst is characterized by comprising 85 percent of modified silicon dioxide as aggregate, 10 percent of Lewis acid, 5 percent of protonic acid and 1 percent of pore-forming agent.

2. An alkylation catalyst according to claim 1, wherein the Lewis acid is in particular aluminium trichloride (AICI)₃) Or yttrium trifluoride (C)₃H₂F₉O₁₀S₃Yb) or dysprosium trifluoride (DyF)₃) Or zinc chloride (ZnCI)₂) The protonic acid comprises concentrated sulfuric acid (H)₂SO₄) Or phosphoric acid (H)₃PO₄) The pore-making agent is methanol (CH)₃OH)。

3. An alkylation catalyst according to claim 2, wherein the pore former is formulated at 1% of the total amount of modified silica plus lewis acid plus protonic acid.

4. A method of preparing an alkylation catalyst, comprising the steps of:

step 1: firstly, adding a quantitative chain extender according to the total amount of methanol for pretreatment;

step 2: feeding the raw materials subjected to chain extension into a No. 1 fixed bed catalytic tower, and heating to 70-85 ℃ to generate a hydrocarbon compound;

step 3: the secondary alkylation reaction is carried out through an alkylation catalyst, so that the carbon chain of the methanol is increased, and the heat value of the fuel is improved;

step 4: mixing the modified silicon dioxide, the Lewis acid, the protonic acid and the pore-forming agent, closing for 6 hours, and then granulating;

step 5: the particles are baked for 4 hours (activation time) at 400-600 ℃.

5. The process of claim 4, wherein the "alkylation catalyst" has dealcoholization molecules to perform etherification and dehydration promotion, thereby performing C-alkylation of olefins, aldehydes, ketones, and the like.

6. The process of claim 5, wherein the Lewis acid provides only a small amount of protons, so that the reaction proceeds smoothly.

7. The process of claim 6, wherein the Lewis acid first forms a molecular complex ion pair, ion complex or alkyl ion with the haloalkane, then the electrophilic protons then form an a-complex with the aromatic ring, and finally the a-complex is deprotonated to introduce an alkyl group onto the aromatic ring.

Technical Field

The invention relates to the technical field of fuel additives, in particular to an alkylation catalyst and a preparation method thereof.

Background

After an engine runs for a long time, carbon deposition is generated, deposits accumulated on an air inlet valve can reduce the sectional area of an air inlet channel, the air inlet efficiency is reduced, the power is reduced, in severe cases, a valve can slow and not close tightly, an oil nozzle can be deposited with carbon, oil injection is not smooth, the atomization quality of fuel oil is reduced, the fuel oil is difficult to completely burn after entering a combustion chamber, the engine is difficult to start, idling is unstable, oil consumption is increased, exhaust emission is deteriorated, and particularly in winter, the conditions are more obvious, so that the condition needs to be improved;

the traditional production process for preparing hydrocarbon from methanol has long flow and low yield, a large amount of industrial wastewater is generated in the production process, the yield of the prepared product of the fuel additive is not high at present, the production safety needs to be enhanced, and the service life of the catalyst needs to be prolonged; to this end, we propose an alkylation catalyst and a process for its preparation.

Disclosure of Invention

The main object of the present invention is to provide an alkylation catalyst and a preparation method thereof to solve the problems mentioned in the background art.

In order to achieve the purpose, the invention adopts the technical scheme that: an alkylation catalyst comprises 85 percent of modified silicon dioxide as aggregate, 10 percent of Lewis acid, 5 percent of protonic acid and 1 percent of pore-forming agent.

Preferably, the Lewis acid is in particular aluminium trichloride (AICI)₃) Or yttrium trifluoride (C)₃H₂F₉O₁₀S₃Yb) or dysprosium trifluoride (DyF)₃) Or zinc chloride (ZnCI)₂) The protonic acid comprises concentrated sulfuric acid (H)₂SO₄) Or phosphoric acid (H)₃PO₄) The pore-making agent is methanol (CH)₃OH)。

Preferably, the pore former is formulated at 1% of the total amount of modified silica plus lewis acid plus protonic acid.

A method of preparing an alkylation catalyst comprising the steps of:

step 1: firstly, adding a quantitative chain extender according to the total amount of methanol for pretreatment;

step 2: feeding the raw materials subjected to chain extension into a No. 1 fixed bed catalytic tower, and heating to 70-85 ℃ to generate a hydrocarbon compound;

step 3: the secondary alkylation reaction is carried out through an alkylation catalyst, so that the carbon chain of the methanol is increased, and the heat value of the fuel is improved;

step 4: mixing the modified silicon dioxide, the Lewis acid, the protonic acid and the pore-forming agent, closing for 6 hours, and then granulating;

step 5: the particles are baked for 4 hours (activation time) at 400-600 ℃.

Preferably, the "alkylation catalyst" has the function of removing alcohol molecules to perform etherification and promote dehydration, so that olefins, aldehydes, ketones and the like are subjected to C-alkylation.

Preferably, the lewis acid provides only a small amount of protons, even if the reaction proceeds smoothly.

Preferably, the lewis acid first forms a molecular complex ion pair, an ionic complex or an alkyl ion with the haloalkane, then these electrophilic protons form an a-complex with the aromatic ring, and finally the a-complex is deprotonated to introduce an alkyl group on the aromatic ring.

The invention has the following beneficial effects:

the alkylation catalyst prepared by the method has the following advantages:

1. the process route is shortened, and the investment of fixed assets is reduced;

2. the traditional deoxidation process is not needed, and the problem that a large amount of industrial wastewater is generated in the production process is solved;

3. the product yield can reach about 94%;

4. the production is carried out at low temperature and normal pressure, and the production safety is improved;

5. the catalyst has long service life and low production cost.

Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

An alkylation catalyst comprises 85 percent of modified silicon dioxide as aggregate, 10 percent of Lewis acid, 5 percent of protonic acid and 1 percent of pore-forming agent.

Wherein the Lewis acid is specifically aluminum trichloride (AICI)₃) Or yttrium trifluoride (C)₃H₂F₉O₁₀S₃Yb) or dysprosium trifluoride (DyF)₃) Or zinc chloride (ZnCI)₂) The protonic acid comprises concentrated sulfuric acid (H)₂SO₄) Or phosphoric acid (H)₃PO₄) The pore-forming agent is methanol (CH)₃OH)。

Wherein the pore-forming agent is prepared according to 1 percent of the total amount of the modified silicon dioxide, the Lewis acid and the protonic acid.

A method of preparing an alkylation catalyst comprising the steps of:

step 1: firstly, adding a quantitative chain extender according to the total amount of methanol for pretreatment;

step 2: feeding the raw materials subjected to chain extension into a No. 1 fixed bed catalytic tower, and heating to 70-85 ℃ to generate a hydrocarbon compound;

step 3: the secondary alkylation reaction is carried out through an alkylation catalyst, so that the carbon chain of the methanol is increased, and the heat value of the fuel is improved;

step 4: mixing the modified silicon dioxide, the Lewis acid, the protonic acid and the pore-forming agent, closing for 6 hours, and then granulating;

step 5: the particles are baked for 4 hours (activation time) at 400-600 ℃.

Wherein, the 'alkylation catalyst' has the dealcoholization molecule to perform the functions of etherification and dehydration promotion, so that olefins, aldehydes, ketones and other C-alkylation are carried out; the Lewis acid only provides a small amount of protons, even if the reaction is smoothly carried out; lewis acid and alkyl halide firstly generate molecular complex ion pairs, ion complexes or alkyl ions, then electrophilic protons and aromatic rings generate a-complexes, and finally the a-complexes are deprotonated to introduce alkyl groups on the aromatic rings.

The invention is characterized in that methanol is converted into C by combining the reactions of catalysis, alkylation, polymerization and the like according to the physicochemical property of the methanol₂-C₅The component (A) forms a mixture of polyhydric alcohol, dimethyl ether and water, further dehydrates the mixture into light olefin, and then forms various paraffin hydrocarbon, aromatic hydrocarbon and cyclane through polymerization and cyclization; solves the problems of long process flow, low yield and large amount of industrial wastewater generated in the production process of the traditional methanol-to-hydrocarbon production process.

Example 2

Aiming at detecting the using effect of the alkylation catalyst prepared by the method, the alkylation catalyst prepared by the method is selected, preferably, the alkylation catalyst comprises 85 percent of modified silicon dioxide as aggregate, 10 percent of Lewis acid, 5 percent of protonic acid and 1 percent of pore-forming agent according to percentage, wherein the Lewis acid is specifically aluminum trichloride (AICI)₃) Or yttrium trifluoride (C)₃H₂F₉O₁₀S₃Yb) or dysprosium trifluoride (DyF)₃) Or zinc chloride (ZnCI)₂) The protonic acid comprises concentrated sulfuric acid (H)₂SO₄) Or phosphoric acid (H)₃PO₄) The pore-forming agent is methanol (CH)₃OH), preparing the pore-forming agent according to 1 percent of the total amount of the modified silicon dioxide, the Lewis acid and the protonic acid;

4 groups of commercial catalysts are selected for use detection comparison, A, B, C, D and E five control groups are randomly set, wherein A, B, C and D are commercial groups, E group is the alkylation catalyst prepared by the method of the invention, and the detection standards are alkylation efficiency (%) and carbon deposition rate (10) of each catalyst under the same working condition^-3mgMin), the test conditions are shown in the table below.

Table one is a comparison of the use test for 5 groups of catalysts:

group of	A	B	C	D	E
						Efficiency of alkylation	94.6	93.9	96.1	96.7	99.4
Rate of carbon deposition	6.25	4.57	6.34	5.53	3.41

As can be seen from the table I, the alkylation catalyst prepared by the method has advantages in alkylation efficiency compared with the commercially available catalyst, and has low carbon deposition efficiency, suitability for long-term use of equipment, strong stability and correspondingly improved popularization value.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.