CN114772834A - Hydrogen-producing acidic water recycling device and method - Google Patents

Abstract

The invention provides a hydrogen production acid water recycling device, which comprises: a mixing tank, a membrane separator and an evaporation dryer; the mixing tank is connected with an acid water inlet pipeline and an alkali liquor inlet pipeline, and is also connected with a mixed liquor outlet pipeline; the inlet end of the membrane separator is connected with the mixed liquid outlet pipeline, and a concentration outlet pipeline is also arranged on the membrane separator; the inlet of the evaporation drier is communicated with a concentration outlet pipeline. The invention also provides a method for recycling the hydrogen-producing acidic water, which comprises the following steps: step S001: introducing acidic water containing carbonate and bicarbonate into a mixing tank, simultaneously introducing alkaline liquor containing hydroxyl into the mixing tank, stirring and neutralizing to generate a carbonate solution and a bicarbonate solution; step S002: introducing the carbonate and bicarbonate solution into a membrane separator for membrane separation to obtain concentrated carbonate and bicarbonate solution; step S003: and (3) introducing the concentrated carbonate and bicarbonate solution into an evaporation drying device to obtain carbonate and bicarbonate crystals.

Description

Hydrogen-producing acidic water recycling device and method

Technical Field

The invention belongs to the field of petrochemical industry, and particularly relates to a hydrogen production acidic water recycling device and method.

Background

The hydrogen production device which prolongs the petroleum belongs to is built in 2013 and 2 months, and handed over in engineering in 2013 and 10 months, and the device is a matching device of a diesel hydrogenation device and comprises a raw material compression and pressure boosting part, a raw material preheating and temperature rising part, a raw material refining hydrodesulfurization part, a water vapor conversion part, a shift reaction and heat recovery part, a steam production system part, a PSA purification part and the like, wherein the raw material refining part adopts ZnO for fine desulfurization to purify raw materials, the conversion part adopts a hydrocarbon-water vapor conversion method to produce hydrogen, and the product part adopts PSA purification and purification technology to produce hydrogen. The hydrogen production capacity of the hydrogen production device is 2 ten thousand standard/hour, the raw materials are catalytic dry gas, hydrogenation dry gas and natural gas, the product is industrial hydrogen with the purity of more than 99.9 mol%, and the produced hydrogen is mainly supplied to the diesel hydrogenation device. The carbon dioxide-containing gas, steam and raw gas enter the converter again after the byproduct acid water is stripped, and CO not dissolved in the inlet water₂Finally, the mixture is subjected to PAS pressure swing adsorption and desorption and hydrogen fuel gas to serve as reformer fuel, and then the reformer fuel is discharged into the atmosphere. The method finally produces a large amount of acid water and simultaneously has higher CO₂And (5) discharging.

Disclosure of Invention

The present invention proposes a hydrogen production acid water recycling apparatus and method to overcome the above problems or at least partially solve or alleviate the above problems.

The invention provides a hydrogen-producing acidic water recycling device, which comprises:

the mixing tank is connected with an acid water inlet pipeline and an alkali liquor inlet pipeline, and is also connected with a mixed liquid outlet pipeline;

the inlet end of the membrane separator is connected with the mixed liquid outlet pipeline, and a concentration outlet pipeline is also arranged on the membrane separator;

and the inlet of the evaporation dryer is communicated with the concentration outlet pipeline.

The hydrogen production acid water recycling device also has the following optional characteristics.

Optionally, the membrane separator is further provided with a water return pipeline, and the water return pipeline is communicated with the mixing tank.

Optionally, a fresh water inlet pipeline is further arranged on the membrane separator.

Optionally, the mixed liquid outlet pipeline is connected with a first circulating pump.

Optionally, the membrane separator further comprises a buffer tank, a concentration buffer pipeline is further arranged on the membrane separator, an inlet of the buffer tank is connected with the concentration buffer pipeline, and an outlet of the buffer tank is communicated with the evaporation dryer through a pipeline.

Optionally, a second circulation pump is further disposed on a pipeline between the buffer tank and the evaporation dryer.

The invention also provides a method for recycling the hydrogen-producing acidic water, which is implemented by adopting the hydrogen-producing acidic water recycling device and comprises the following steps:

step S001: introducing acidic water containing carbonate and bicarbonate radical into a mixing tank, simultaneously introducing alkaline liquor containing hydroxyl radical into the mixing tank, stirring and neutralizing to generate a carbonate and bicarbonate solution;

step S002: introducing the carbonate and bicarbonate solution into a membrane separator for membrane separation to obtain concentrated carbonate and bicarbonate solution;

step S003: and (3) introducing the concentrated carbonate and bicarbonate solution into an evaporation drying device to obtain carbonate and bicarbonate crystals.

In step S001, the alkali solution is sodium hydroxide.

The hydrogen production acid water recycling device and the process thereof of the invention containHas higher CO₂The acid water is neutralized and converted into sodium bicarbonate or sodium carbonate solution, the solution can be directly taken as a product to be discharged from a device, and can also be prepared into sodium bicarbonate or sodium carbonate crystals by membrane separation, so that the problem of acid water discharge of a hydrogen production device is solved, and the environmental CO is reduced₂And (5) discharging.

Drawings

Fig. 1 is a schematic structural view of an embodiment of the hydrogen-producing acidic water recycling apparatus according to the present invention.

In the above figures: 1, a mixing tank; 2 an acid water inlet pipeline; 3 an alkali liquor inlet pipeline; 4, a mixed liquid outlet pipeline; 5, a membrane separator; 6 a concentration outlet pipeline; 7, an evaporation dryer; 8, a water return pipeline; 9 introducing fresh water into a pipeline; 10 a first circulation pump; 11, a cache tank; 12 a concentration cache pipeline; 13 a second circulation pump; 14 a return water bypass.

Detailed Description

Example 1

Referring to fig. 1, an embodiment of the present invention provides a hydrogen production acidic water recycling apparatus, including: a mixing tank 1, a membrane separator 5 and an evaporation dryer 7; the mixing tank 1 is connected with an acid water inlet pipeline 2 and an alkali liquor inlet pipeline 3, and the mixing tank 1 is also connected with a mixed liquor outlet pipeline 4; the inlet end of the membrane separator 5 is connected with the mixed liquid outlet pipeline 4, and the membrane separator 5 is also provided with a concentrated outlet pipeline 6; the inlet of the evaporation dryer 7 is communicated with the concentration outlet pipeline 6.

The hydrogen production device produces high-content CO₂The acidic water is introduced into a mixing tank 1 through an acidic water inlet pipeline 2, a sodium hydroxide solution is introduced through an alkali liquor inlet pipeline 3, an acid-base corrosion prevention stirring impeller is arranged in the mixing tank 1, the sodium hydroxide solution is stirred by the acid-base corrosion prevention stirring impeller to be neutralized with the acidic water, and a PH detector is arranged on the wall of the mixing tank 1 and used for controlling and adjusting the PH in the device; the pH parameter is adjusted and controlled to generate sodium bicarbonate or sodium carbonate solution which can be directly taken as a product to be discharged from the device. The reaction formula is as follows:

H⁺+HCO₃ ^-+NaOH＝NaHCO₃+H₂O

2H⁺+CO₃ ^2-+NaOH＝NaCO₃+2H₂O

the sodium bicarbonate or sodium carbonate solution is injected from the top of the membrane separator 5 through the mixed solution outlet pipeline 4, the upper layer of the filtering membrane in the membrane separator 5 is the sodium bicarbonate or sodium carbonate solution with higher concentration, the mixed solution outlet pipeline 4 connected with the upper side area of the filtering membrane in the membrane separator 5 is communicated with the evaporation dryer 7, and the high-concentration sodium bicarbonate or sodium carbonate solution separated by the membrane separator 5 can be introduced into the evaporation dryer 7 to be prepared into sodium bicarbonate or sodium carbonate crystals.

Example 2

Referring to fig. 1, in addition to embodiment 1, a water return line 8 is further provided on the membrane separator 5, and the water return line 8 leads back to the mixing tank 1.

The lower area of the filtering membrane of the membrane separator 5 is connected with a return pipe 8, the return pipe 8 is connected with the mixing tank 1, if the membrane fails, the water separated by the filtering membrane of the membrane separator 5 flowing out can be returned to the mixing tank 1, and can also be discharged to other places through a return bypass 14 on the return pipe 8.

Example 3

Referring to fig. 1, on the basis of embodiment 1, a fresh water inlet line 9 is also provided on the membrane separator 5.

The membrane separator 5 can also be purged from the concentrate outlet line 6 by fresh water via fresh water inlet line 9.

Example 4

Referring to fig. 1, in example 1, a first circulation pump 10 is connected to the mixed liquid outlet pipe 4.

The first circulating pump 10 on the mixed liquid outlet pipe 4 can pump the mixed liquid in the mixing tank 1 to the membrane separator 5.

Example 5

Referring to fig. 1, on the basis of embodiment 1, the membrane separator further includes a buffer tank 11, the membrane separator 5 is further provided with a concentration buffer pipeline 12, an inlet of the buffer tank 11 is connected to the concentration buffer pipeline 12, and an outlet of the buffer tank 11 is communicated to the evaporation dryer 7 through a pipeline.

Sodium bicarbonate or sodium carbonate solution is introduced into the evaporation dryer 7 and then is evaporated by steam tracing to obtain sodium bicarbonate or sodium carbonate crystals, and since only a certain amount of high-concentration sodium bicarbonate or sodium carbonate solution can be introduced into the evaporation dryer 7 each time, the concentration buffer tank 11 is provided for temporarily storing the sodium bicarbonate or sodium carbonate solution.

Example 6

Referring to fig. 1, on the basis of embodiment 5, a second circulation pump 13 is further disposed on the pipeline between the buffer tank 11 and the evaporation dryer 7.

The second circulation pump 13 can feed the high-concentration sodium bicarbonate or sodium carbonate solution stored in the buffer tank 11 into the evaporation dryer 7.

Example 7

The embodiment of the invention also provides a hydrogen production acidic water recycling method, which is implemented by adopting the hydrogen production acidic water recycling device in any one of the embodiments and comprises the following steps: step S001: introducing acidic water containing carbonate and bicarbonate radical into a mixing tank 1, simultaneously introducing alkaline liquor containing hydroxyl radical into the mixing tank 1, stirring and neutralizing to generate a carbonate and bicarbonate solution; step S002: feeding the carbonate and bicarbonate solution into a membrane separator 5 to separate the concentrated carbonate and bicarbonate solution by a membrane; step S003: and (3) introducing the concentrated carbonate and bicarbonate solution into an evaporation drying device 7 to obtain carbonate and bicarbonate crystals.

The hydrogen-producing acidic water mainly comprises the following components: CO, CO₂、CH₄、N₂、H₂O, wherein CO₂(wt%) content about: 11 percent, the flow rate of acid water entering the device is 14t/h, the temperature is 70 ℃, alkali liquor is fed by 30 percent NaOH solution at normal temperature, the feeding amount is about 3.5t/h, the temperature after mixing is about 60 ℃, the mixture is mixed in a mixing tower for about 20 minutes and discharged, the discharge amount is controlled at 17.5t/h, the mixture is separated by a membrane separator, wherein the separation rate of the membrane is 98 percent, and the NaCO can be filtered and concentrated for multiple times to obtain about 30 percent NaCO at 40 DEG C₃Concentrated solution, NaCO₃The concentrated solution enters a drier heated by steam, and a stirrer is arranged in the drierMixer for preventing NaCO₃Agglomerating, and adding NaCO into a drier under the continuous stirring of a stirrer₃Evaporating the concentrated solution to obtain NaCO₃The crystal powder can be packaged in woven bag with moisture-proof lining.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims. The components and structures of the present embodiments that are not described in detail are known in the art and are not described in detail herein.

Claims (8)

1. The hydrogen production acid water recycling device is characterized by comprising:

the device comprises a mixing tank (1), wherein the mixing tank (1) is connected with an acidic water inlet pipeline (2) and an alkaline liquid inlet pipeline (3), and the mixing tank (1) is also connected with a mixed liquid outlet pipeline (4);

the inlet end of the membrane separator (5) is connected with the mixed liquid outlet pipeline (4), and the membrane separator (5) is also provided with a concentration outlet pipeline (6);

the inlet of the evaporation drier (7) is communicated with the concentration outlet pipeline (6).

2. The hydrogen-producing acidic water recycling device according to claim 1, wherein the membrane separator (5) is further provided with a water return pipeline (8), and the water return pipeline (8) is communicated back to the mixing tank (1).

3. The hydrogen-producing acidic water recycling device according to claim 1, characterized in that the membrane separator (5) is further provided with a fresh water inlet pipeline (9).

4. The hydrogen-producing acidic water recycling device according to claim 1, wherein the mixed liquid outlet pipeline (4) is connected with a first circulating pump (10).

5. The hydrogen-producing acidic water recycling device according to claim 1, further comprising a buffer tank (11), wherein a concentration buffer pipeline (12) is further disposed on the membrane separator (5), an inlet of the buffer tank (11) is connected to the concentration buffer pipeline (12), and an outlet of the buffer tank (11) is communicated to the evaporation dryer (7) through a pipeline.

6. The hydrogen-producing acidic water recycling device according to claim 5, wherein a second circulating pump (13) is further arranged on a pipeline between the buffer tank (11) and the evaporation dryer (7).

7. A method for recycling hydrogen-producing acidic water, which is implemented by using the apparatus for recycling hydrogen-producing acidic water according to any one of claims 1 to 6, and comprises the following steps:

step S001: introducing acidic water containing carbonate and bicarbonate radical into a mixing tank, simultaneously introducing alkaline liquor containing hydroxyl radical into the mixing tank, stirring and neutralizing to generate a carbonate and bicarbonate solution;

step S002: introducing the carbonate and bicarbonate solution into a membrane separator for membrane separation to obtain concentrated carbonate and bicarbonate solution;

step S003: and (3) introducing the concentrated carbonate and bicarbonate solution into an evaporation drying device to obtain carbonate and bicarbonate crystals.

8. The method for recycling hydrogen-producing acidic water according to claim 7, wherein in step S001, the alkali solution is sodium hydroxide.

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