阅读说明：本技术 一种采用多碳烯烃合成多碳硫醇的生产装置 (Production device for synthesizing polycarbon mercaptan by adopting polycarbon olefin ) 是由 陆继长 冯斯佑 罗永明 朱松山 李英豪 邓维华 方健 于 2021-03-10 设计创作，主要内容包括：本发明公开了一种采用多碳烯烃合成多碳硫醇的生产装置,其包括气瓶Ⅰ、气瓶Ⅱ、循环单元、进液泵、气液混合器、加热炉、合成反应器、分布器、垫板、冷凝器、大容量储液器、微量储液器、尾气吸收装置；本发明可实现对催化剂多条件的原位预处理、满足三相催化的多种反应条件,可连续化运行、间隔时间内微量化采样,其具有功能性强、安全性高、稳定性好的特点,特别适用于硫化氢与多碳烯烃加成制多碳硫醇反应。(The invention discloses a production device for synthesizing polycarbon mercaptan by adopting polycarbon olefin, which comprises a gas cylinder I, a gas cylinder II, a circulation unit, a liquid inlet pump, a gas-liquid mixer, a heating furnace, a synthesis reactor, a distributor, a base plate, a condenser, a large-capacity liquid storage device, a micro-liquid storage device and a tail gas absorption device, wherein the gas cylinder I is connected with the gas cylinder II; the method can realize in-situ pretreatment of multiple conditions of the catalyst, meet multiple reaction conditions of three-phase catalysis, can continuously run and sample in a micro manner within an interval time, has the characteristics of strong functionality, high safety and good stability, and is particularly suitable for the reaction of preparing the polycarbon mercaptan by adding the hydrogen sulfide and the polycarbon olefin.)

1. A production device for synthesizing polycarbon mercaptan by adopting polycarbon olefin is characterized in that: the device comprises a gas cylinder I (1), a gas cylinder II (2), a circulating unit (3), a liquid inlet pump (7), a gas-liquid mixer (8), a heating furnace (9), a synthesis reactor (10), a distributor (12), a base plate (13), a condenser (14), a large-capacity liquid storage device (16), a micro liquid storage device (18) and a tail gas absorption device (22); the gas cylinder I (1) is communicated with a gas-liquid mixer (8) through a pipeline, and a pressure reducing valve I (4), a flowmeter I (5) and a two-way valve I (6) are sequentially arranged on the pipeline; the gas cylinder II (2) is communicated with the circulating unit (3), the circulating unit (3) is communicated with a gas-liquid mixer (8) through a pipeline, and a pressure reducing valve II, a flow meter II and a two-way valve II are sequentially arranged on the pipeline; the liquid inlet pump (7) is connected with a gas-liquid mixer (8), a synthesis reactor (10) is arranged in a heating furnace (9), the gas-liquid mixer (8) is connected with a condenser (14) through the synthesis reactor (10), one path of the condenser (14) is communicated with the circulation unit (3) through a backpressure valve (20) and a three-way valve II (21), and the other path is connected with a large-capacity liquid reservoir (16) through a three-way valve I (15); the micro liquid accumulator (18) is connected with the three-way valve I (15), and the upper part of the micro liquid accumulator (18) is connected with the large-capacity liquid accumulator (16) through the single-phase stop valve (17); the bottoms of the large-capacity liquid storage device (16) and the trace liquid storage device (18) are respectively provided with a vent valve, and the tail gas absorption device (22) is connected with the three-way valve II (21).

2. The apparatus for producing a polycarbomercaptan as defined in claim 1, wherein: the synthesis reactor (10) comprises a shell, a distributor (12) and a backing plate (13), wherein the top and the bottom of the shell are respectively provided with a feed inlet and a discharge outlet, the backing plate (13) is arranged at the bottom of the shell, the distributor (12) is arranged on the backing plate (13), a catalyst is placed on the distributor, and the other distributor is arranged above the catalyst; the shell is sleeved with a cooling cavity, and the cooling cavity is connected with a circulating water refrigerating device (23).

3. The apparatus for producing a polycarbomercaptan as defined in claim 1, wherein: the circulating unit consists of a gas storage tank and a gas pressurizing pump, the gas bottle II (2) is connected with the gas pressurizing pump through the gas storage tank, and the gas pressurizing pump is connected with the pressure reducing valve II.

4. The apparatus for producing a polycarbomercaptan as defined in claim 2, wherein: the backing plate (13) is of a spool structure and is provided with a through hole.

5. The apparatus for producing a polycarbomercaptan as defined in claim 1, wherein: the tail gas absorption device (22) is formed by connecting a container filled with alkali liquor and a container filled with absolute ethyl alcohol in series, wherein the alkali liquor is saturated sodium hydroxide.

Technical Field

The invention belongs to the field of chemical catalysis, and particularly relates to a production device for synthesizing polycarbon mercaptan by adopting polycarbon olefin.

Background

At present, isobutene with low polymerization degree such as diisobutylene, triisobutene, tetraisobutylene and the like can be produced in large quantities in China, however, the downstream products are few at present, the resource utilization is insufficient, and simultaneously, a large quantity of imported mercaptan products, particularly tertiary dodecyl mercaptan, are still needed in China. Therefore, the method can be feasible for converting isobutene with low polymerization degree, which is guaranteed in China, into mercaptan products with high added value and urgent need. Traditional gas-liquid-solid three-phase reaction devices are mostly applied to low-toxicity and low-risk reactions such as biomass conversion, and a catalytic reaction device for feeding or discharging odorous products with high toxicity and high volatility is reported, and particularly relates to continuous and long-time synthesis of odorous chemicals such as mercaptan.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a production device for synthesizing polycarbon mercaptan by adopting polycarbon olefin, which comprises a gas cylinder I, a gas cylinder II, a circulation unit, a liquid inlet pump, a gas-liquid mixer, a heating furnace, a synthesis reactor, a distributor, a base plate, a condenser, a large-capacity liquid storage device, a trace liquid storage device and a tail gas absorption device, wherein the gas cylinder I is connected with the gas cylinder II through the circulation unit; the gas cylinder I is communicated with the gas-liquid mixer through a pipeline, and a pressure reducing valve I, a flowmeter I and a two-way valve I are sequentially arranged on the pipeline; the gas cylinder II is communicated with the circulating unit, the circulating unit is communicated with the gas-liquid mixer through a pipeline, and a pressure reducing valve II, a flow meter II and a two-way valve II are sequentially arranged on the pipeline; the liquid inlet pump is connected with a gas-liquid mixer, the synthesis reactor is arranged in the heating furnace, the gas-liquid mixer is connected with a condenser through the synthesis reactor, one path of the condenser is communicated with the circulation unit through a back pressure valve and a three-way valve II, and the other path of the condenser is connected with a high-capacity liquid storage device through a three-way valve I; the micro liquid accumulator is connected with the three-way valve I, and the upper part of the micro liquid accumulator is connected with the large-capacity liquid accumulator through the single-phase stop valve; and the bottoms of the trace liquid storage device and the large-capacity liquid storage device are both provided with emptying valves, and the tail gas absorption device is connected with the three-way valve II.

The synthesis reactor comprises a shell, a distributor and a base plate, wherein a feed inlet and a discharge outlet are respectively formed in the top and the bottom of the shell, the base plate is arranged at the bottom of the shell, the distributor is arranged on the base plate, a catalyst is placed on the distributor, and the other distributor is arranged above the catalyst; a cooling cavity is sleeved outside the shell and connected with circulating water refrigeration equipment; the backing plate is of a spool structure and is provided with a through hole.

The circulating unit consists of a gas storage tank and a gas pressurizing pump, the gas cylinder II is connected with the gas pressurizing pump through the gas storage tank, and the gas pressurizing pump is connected with the pressure reducing valve II.

The tail gas absorption device is formed by connecting a container filled with alkali liquor and a container filled with absolute ethyl alcohol in series, wherein the alkali liquor is saturated sodium hydroxide; the front end of the tail gas absorption device can be connected with a chromatographic analyzer for analyzing the components of the tail gas.

All parts in the device, which are in direct contact with the feeding and discharging materials, are subjected to anticorrosive treatment and are made of 316L stainless steel.

The device controls the reaction pressure through the linkage of the circulating unit and the backpressure valve; the flow rate of the feeding material and the feeding molar ratio are controlled by the linkage of a flow meter and a liquid inlet pump; the raw materials are fully mixed in a gas-liquid mixer; the fully mixed raw materials enter a synthesis reactor, the reactor is a cylinder with a jacket, low-temperature constant-temperature water flows in the jacket, a heating furnace is arranged outside the jacket, a distributor, a catalyst, a distributor and a base plate are respectively arranged in the reactor from top to bottom, the upper distributor plays a role in promoting the uniform distribution of the fed materials, the lower distributor plays a role in fixing the catalyst, and the base plate adjusts the height of a catalyst bed; reaction product carries out the gas-liquid separation after the condensation, gas can get into circulation unit through three-way valve II and participate in the reaction once more, also can get into tail gas absorbing device and absorb, liquid passes through the continuous reservoir that gets into the large capacity of three-way valve I, can also be interrupted and get into the trace reservoir, be used for sample analysis, wherein trace reservoir upper portion links to each other with the large capacity reservoir through single-phase stop valve, can avoid trace reservoir storage excessive and lead to in system collapse and the large capacity reservoir the phenomenon of gas backward flow to the trace reservoir to take place, after the reaction, carry out the evacuation through the atmospheric relief valve.

The device has a simple structure, is safe and environment-friendly, can realize continuous synthesis of high-risk and high-toxicity chemical products, can realize an operating temperature of-20-800 ℃, can accurately control reaction conditions, can realize in-situ pretreatment of multiple conditions of the catalyst, can realize micro sampling through a trace liquid storage device in the reaction, is convenient to detect, and is suitable for industrial production and market popularization and application.

Drawings

FIG. 1 is a schematic diagram of the apparatus of the present invention;

FIG. 2 is a schematic view of a pad structure;

FIG. 3 is a schematic top view of the backing plate;

FIG. 4 is an enlarged view of the micro reservoir;

in the figure: the system comprises a gas cylinder I1, a gas cylinder II 2, a circulation unit 3, a pressure reducing valve I4, a flow meter I5, a two-way valve I6, a liquid inlet pump 7, a gas-liquid mixer 8, a heating furnace 9, a synthesis reactor 10, a catalyst 11, a distributor 12, a backing plate 13, a condenser 14, a three-way valve I15, a large-capacity liquid storage device 16, a one-way stop valve 17, a trace liquid storage device 18, an emptying valve 19, a back pressure valve 20, a three-way valve II 21, a tail gas absorption device 22 and circulating water refrigeration equipment 23.

Detailed Description

The invention will be described in more detail below with reference to the drawings and examples, but the scope of the invention is not limited thereto,

example 1: as shown in fig. 1-4, the production device for synthesizing the polycarbon mercaptan by using the polycarbon olefin comprises a gas cylinder I1, a gas cylinder II 2, a circulation unit 3, a liquid inlet pump 7, a gas-liquid mixer 8, a heating furnace 9, a synthesis reactor 10, a distributor 12, a base plate 13, a condenser 14, a large-capacity liquid storage device 16, a trace liquid storage device 18 and a tail gas absorption device 22; the gas cylinder I1 is communicated with a gas-liquid mixer 8 through a pipeline, and a pressure reducing valve I4, a flowmeter I5 and a two-way valve I6 are sequentially arranged on the pipeline; the circulating unit consists of a gas storage tank and a gas booster pump, the gas cylinder II 2 is connected with the gas booster pump through the gas storage tank, the gas booster pump is communicated with the gas-liquid mixer 8 through a pipeline, and a pressure reducing valve II, a flowmeter II and a two-way valve II are sequentially arranged on the pipeline; the liquid inlet pump 7 is connected with a gas-liquid mixer 8, the synthesis reactor 10 is arranged in a heating furnace 9, the synthesis reactor 10 comprises a shell, a distributor 12 and a base plate 13, the top and the bottom of the shell are respectively provided with a feed inlet and a discharge outlet, the shell is a cylinder with a jacket, a cooling cavity is arranged in the jacket, the base plate 13 is arranged at the bottom of the shell, the base plate 13 is of a I-shaped wheel structure and is provided with a through hole, the distributor 12 is arranged on the base plate 13, the catalyst is placed on the distributor, the other distributor is arranged above the catalyst, and the cooling cavity is connected with a circulating water refrigeration device 23; the gas-liquid mixer 8 is connected with a condenser 14 through a synthesis reactor 10, one path of the condenser 14 is communicated with the circulation unit 3 through a backpressure valve 20 and a three-way valve II 21, the other path of the condenser is connected with a large-capacity liquid storage device 16 through a three-way valve I15, an emptying valve is arranged at the bottom of the large-capacity liquid storage device 16, and the large-capacity liquid storage device is a 10L storage tank; the micro liquid storage device 18 comprises a shell with the capacity of 5mL, the top and the bottom of the shell are provided with a liquid inlet and a liquid outlet I, the liquid inlet is communicated with a three-way valve I15, the liquid outlet is provided with a vent valve 19, the upper part of the shell is provided with a liquid outlet II, the liquid outlet II is connected with a large-capacity liquid storage device 16 through a single-phase stop valve 17, and a tail gas absorption device 22 is connected with a three-way valve II 21;

the device is illustrated by taking the synthesis of tert-octyl mercaptan by adding diisobutylene into hydrogen sulfide at low temperature and low pressure as an example:

when in use, the backing plate 13, the distributor 12, the Amberlyst-35 catalyst and the distributor are sequentially placed into a synthesis reactor, a gas cylinder I1 filled with nitrogen, a pressure reducing valve I4, a flow meter I5 and a two-way valve I6 are opened, wherein the flow rate of the flow meter I is set to be 50mL/min, the temperature of a heating furnace 9 is adjusted to 110 ℃, the catalyst is heated overnight under the nitrogen atmosphere, then the reaction pressure is adjusted to be 1.0Mpa, and the airtightness is checked; opening a circulating water refrigeration device 23 to reduce the temperature of the synthesis reactor 10 to 10 ℃, and closing a gas cylinder I1, a pressure reducing valve I4, a flow meter I5 and a two-way valve I6 on a pipeline from the gas cylinder 1 to a gas-liquid mixer 8;

opening a gas cylinder II 2 filled with hydrogen sulfide gas, a gas storage tank and a gas pressure pump in the circulating unit 3, a pressure reducing valve II, a flow meter II and a two-way valve II on a pipeline from the gas cylinder II 2 to a gas-liquid mixer 8, introducing hydrogen sulfide into the gas-liquid mixer 8 at 65mL/min, simultaneously introducing diisobutylene into the gas-liquid mixer 8 at 15mL/h flow rate through a liquid inlet pump 7, uniformly mixing the gas and the liquid in the gas-liquid mixer 8, then introducing the gas and the liquid into a synthesis reactor 10 to be in contact reaction with a catalyst, after the reaction is finished, introducing a reaction product into a condenser 14 at 5 ℃ for cooling, introducing the liquid into a large-capacity liquid storage tank 16 through a three-way valve I15, and returning the gas to the gas storage tank of the circulating unit through a back pressure; during sampling, a passage between the three-way valve I15 and the micro liquid reservoir 18 is opened, and the passage is closed after sampling is finished; after 4 hours of reaction, sampling and analyzing that the conversion rate of the diisobutylene is 93.6 percent, the selectivity of the triisobutene in the product is 8.8 percent, the selectivity of the tert-octyl mercaptan is 88.4 percent, the selectivity of the tert-dodecyl mercaptan is 2.8 percent, and no other side products are generated; when the catalyst is replaced or the gas of the system is discharged, the pipeline communicated with the tail gas absorption device is opened.

Example 2: the structure of the device of the embodiment is the same as that of the embodiment 1, and the difference is that: soaking a proper amount of zirconium nitrate on active alumina, adding sulfuric acid with the concentration of 1M for vulcanization, and then calcining at the high temperature of 800 ℃ in a muffle furnace at 500 ℃ for in-situ treatment at the temperature of 300 ℃ overnight, then reducing the temperature to reaction temperature, controlling hydrogen sulfide to be introduced into a synthesis reactor 10 through a flow meter II at a rate of 30mL/min, introducing triisobutene into the synthesis reactor 10 through a liquid inlet pump 7 at a rate of 6mL/h, fully mixing the hydrogen sulfide and the triisobutene, and then carrying out contact reaction on the hydrogen sulfide and the triisobutene, wherein the reaction pressure is 0.8Mpa, and the reaction temperature is 180 ℃; after 4h, a sample was taken for analysis to show that the triisobutene conversion was 83%, the tert-butyl mercaptan selectivity was 53.2%, the tert-octyl mercaptan selectivity was 26.3%, the tert-dodecyl mercaptan selectivity was 20.5%, and no other mercaptans were formed.